WO2018170927A1 - Integrated secondary cell, and manufacturing method thereof - Google Patents

Integrated secondary cell, and manufacturing method thereof Download PDF

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Publication number
WO2018170927A1
WO2018170927A1 PCT/CN2017/078205 CN2017078205W WO2018170927A1 WO 2018170927 A1 WO2018170927 A1 WO 2018170927A1 CN 2017078205 W CN2017078205 W CN 2017078205W WO 2018170927 A1 WO2018170927 A1 WO 2018170927A1
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positive electrode
active material
secondary battery
integrated
current collector
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PCT/CN2017/078205
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French (fr)
Chinese (zh)
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唐永炳
蒋春磊
方月
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深圳先进技术研究院
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Priority to PCT/CN2017/078205 priority Critical patent/WO2018170927A1/en
Publication of WO2018170927A1 publication Critical patent/WO2018170927A1/en

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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • the present invention relates to the field of secondary battery technology, and in particular to an integrated secondary battery and a method of fabricating the same.
  • Lithium ion secondary batteries have the advantages of high operating voltage, high energy and power density, light weight, long life, no memory effect, low self-discharge effect, etc., and have been widely used in various electronic devices, such as mobile phones, digital cameras, notebook computers. , power tools, drones, electric cars, etc. In recent years, with the rapid development of power tools, car models, aircraft models, ship models, drones, electric vehicles and other industries, the performance requirements for lithium-ion batteries are getting higher and higher. Because these devices not only require high energy density and longevity of lithium ion batteries, but also require lithium ion batteries to meet the high rate performance of high current charge and discharge.
  • the general commercial lithium-ion battery has poor rate performance, usually only reaches 3C, resulting in long charging and discharging time, poor current discharge performance, and equipment can not achieve instantaneous or continuous high power output; and large current discharge will cause the battery internal temperature to be short.
  • the sharp increase in time and the risk of thermal runaway safety will result in a sharp drop in battery life.
  • the low rate performance of lithium-ion batteries is mainly caused by low electron and ion transport speeds during charge and discharge.
  • researchers have tried various methods, such as designing active materials with high ion diffusion coefficients. Use nanomaterials to shorten the diffusion distance of electrons and ions, construct a three-dimensional network structure to provide an effective path for the diffusion of electrons and ions, and add conductive agents (graphene, carbon nanotubes, etc.) and coated conductive layers (usually carbon layers). Wait. Although these methods can improve the rate performance of the electrode material, it is difficult to achieve ultra-high rate performance of the full battery due to limitations in the structure of the battery and the manufacturing process.
  • the present invention provides an integrated secondary battery in which a positive electrode current collector is directly disposed on a surface of a positive electrode active material, so that a positive electrode current collector and a positive electrode active material have a good relationship between them. Contact can effectively reduce the contact resistance of the battery, thereby improving the rate performance of the battery.
  • the present invention provides an integrated secondary battery including an integrated battery body, a battery case, and an electrolyte, the integrated battery body including a positive electrode, a porous separator, and a negative electrode disposed in sequence;
  • the porous separator includes opposite first and second surfaces;
  • the positive electrode includes a positive active material layer disposed on the first surface and a positive current collector disposed on the positive active material layer;
  • the negative electrode includes a metal film layer simultaneously serving as a negative electrode current collector and a negative electrode active material; the electrolyte solution is filled between the positive electrode and the negative electrode.
  • the metal film layer is disposed on the second surface by deposition.
  • the positive active material layer is disposed on the first surface by coating; the positive current collector is disposed on the positive active material layer by deposition.
  • the metal film layer has a three-dimensional porous structure in a thickness direction thereof, and the porous pore size is from 20 nm to 100 ⁇ m.
  • the material of the metal film layer is a metal material
  • the metal material comprises any one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium and lead, or contains at least one of the above metal elements.
  • the porous membrane comprises a mixed layer extending from the second surface toward the inside of the porous membrane, and the metal material is adhered to the pores of the mixed layer, and the mixed layer has a thickness of 20 nm to 10 ⁇ m. .
  • the thickness of the metal film layer is from 0.1 ⁇ m to 300 ⁇ m.
  • the positive electrode current collector has a thickness of 0.1 ⁇ m to 300 ⁇ m, and the positive electrode active material layer has a thickness of 10 ⁇ m to 100 ⁇ m.
  • the positive electrode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials.
  • the electrolyte comprises an electrolyte and a solvent, the electrolyte comprising one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt and a calcium salt; wherein the electrolyte has a concentration of 0.1- 10 mol / L.
  • the positive electrode current collector is directly disposed on the surface of the positive electrode active material, the positive electrode current collector and the positive electrode active material have good contact, and there may be
  • the utility model reduces the contact resistance of the battery, thereby improving the rate performance of the battery; the integrated secondary battery of the invention has a simple structure, can greatly simplify the assembly process of the battery, and only needs to directly place the integrated battery structure of the invention in the battery casing
  • the electrolyte can be added for packaging, which is simple and convenient.
  • a second aspect of the embodiments of the present invention provides a method for preparing an integrated secondary battery, comprising the following steps:
  • the positive electrode active material is weighed in a certain ratio, and mixed well by adding a suitable solvent to form a uniform slurry; then the slurry is uniformly coated on the first surface to obtain a positive electrode active material layer, and then on the positive electrode active material layer.
  • the integrated battery body is then placed in a battery case in an inert gas or waterless environment, and the electrolyte is added and packaged to obtain an integrated secondary battery.
  • the manner of depositing includes one or more of vapor deposition, cold spray, and thermal spray, and the vapor deposition includes at least one of physical vapor deposition and chemical vapor deposition.
  • the coating method comprises one or more of knife coating, spin coating, spray coating, roll coating and extrusion coating.
  • the method for preparing a secondary battery provided by the second aspect of the invention has a simple process and is suitable for large-scale production.
  • FIG. 1 is a schematic structural view of an integrated secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a charge-discharge curve (a) of an integrated aluminum-graphite dual ion battery prepared according to Example 1 of the present invention at a ratio of 1, 10, and 30 C, and a charge-discharge curve at a rate of 60, 90, and 120 C (b). , the rate performance of the secondary battery at a ratio of 1-120C and the corresponding coulombic efficiency (c), the cycle performance curve of the cycle of 1500 cycles at 60C rate (d);
  • Example 3 is a cycle performance curve of an aluminum-graphite secondary battery prepared in Example 1 of the present invention at a super high rate of 120 C for 200 cycles;
  • Example 4 is a scanning electron micrograph of an aluminum-graphite secondary battery prepared in Example 1 of the present invention, (a) a battery negative electrode The porous structure of the negative aluminum film layer at the interface with the porous membrane, (b) the interface morphology of the positive electrode current collector aluminum film layer and the positive electrode graphite active material;
  • Example 5 is an electrochemical impedance spectroscopy spectrum of an aluminum-graphite secondary battery (circle) and a conventional aluminum-graphite dual ion battery (dot) prepared in Example 1 of the present invention
  • Example 6 is a comparison diagram of energy density and power density of an aluminum-graphite secondary battery and a conventional energy storage device (a lithium ion battery, a lead acid battery, a nickel hydrogen battery, and a super capacitor) prepared in Example 1 of the present invention.
  • a conventional energy storage device a lithium ion battery, a lead acid battery, a nickel hydrogen battery, and a super capacitor
  • a first aspect of an embodiment of the present invention provides an integrated secondary battery including an integrated battery body, a battery case, and an electrolyte, wherein the integrated battery body includes a positive electrode, a porous separator, and a negative electrode disposed in sequence;
  • the separator includes a first surface and a second surface disposed opposite to each other;
  • the positive electrode includes a positive active material layer disposed on the first surface and a positive current collector disposed on the positive active material layer;
  • the negative electrode is disposed at On the second surface, the negative electrode includes a metal film layer serving as a negative electrode current collector and a negative electrode active material at the same time; the electrolyte solution is filled between the positive electrode and the negative electrode.
  • the cathode active material has a layered crystal structure.
  • the cathode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials.
  • the carbon material comprises one or more of a graphite-based carbon material, a glassy carbon, a carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotubes, and graphene.
  • the graphite-based carbon material includes one or more of natural graphite, expanded graphite, artificial graphite, flake graphite, spherical graphite, mesocarbon microbead graphite, pyrolytic graphite, high-orientation graphite, and three-dimensional graphite sponge.
  • the sulfide is selected from the group consisting of molybdenum disulfide, tungsten disulfide, vanadium disulfide, and disulfide.
  • the nitride is selected from the group consisting of hexagonal boron nitride and carbon doped hexagonal boron nitride
  • the oxide is one or more selected from the group consisting of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, and manganese oxide
  • the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide, and silicon carbide.
  • the positive electrode active material layer further includes a conductive agent and a binder
  • the ratio of the positive electrode active material to the conductive agent and the binder is not particularly limited, and the conventional ratio in the art may be used, such as
  • the positive electrode active material has a mass content of 60% to 90%
  • the conductive agent has a mass content of 0.1% to 30%
  • the binder has a mass content of 0.5% to 15%.
  • the conductive agent is not particularly limited, and may be one or more of conventional materials available in the art, such as conductive carbon black, conductive acetylene black, Super P conductive carbon sphere, conductive graphite KS6, carbon nanotube, graphene, and the like.
  • the binder to be added to the positive electrode active material layer is also not particularly limited, and conventional materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and SBR rubber may be used.
  • conventional materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and SBR rubber may be used.
  • polyolefins, and the like are examples of polyolefins, and the like.
  • the positive electrode active material layer is disposed on the first surface by coating; the coating manner includes blade coating, spin coating, spray coating, roll coating, and extrusion coating. One or more.
  • the cathode current collector is disposed on the surface of the cathode active material by deposition.
  • the deposition technique used for depositing the cathode current collector may be selected from at least one of a physical vapor deposition technique and a chemical vapor deposition technique, and a composite of one or more of a cold spray technique and a thermal spray technique;
  • the physical vapor deposition technique can be selected from the group consisting of evaporation, sputtering, arc ion plating, etc., and further optionally using sputtering technology.
  • the positive electrode current collector prepared by the deposition technique is a film material, has good flexibility, and can be used for preparing a flexible secondary battery.
  • the material of the cathode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, and lead, or an alloy containing at least one of the above metal elements, or contains a composite material of at least one of the above metal elements.
  • the thickness of the positive electrode active material layer is from 10 ⁇ m to 100 ⁇ m; the thickness of the positive electrode current collector is from 0.1 ⁇ m to 300 ⁇ m, and optionally, the thickness of the positive electrode current collector is from 0.1 ⁇ m to 100 ⁇ m.
  • the metal film layer is disposed on the second surface by deposition.
  • the metal film layer prepared by the deposition technology of the invention is a film material, has good flexibility, and can be used for preparing a flexible secondary battery.
  • the material of the metal film layer is a metal material
  • the metal material includes any one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium, and lead, or contains at least one kind of An alloy of the above metal elements or a composite material containing at least one of the above metal elements.
  • the alloy may be selected from the group consisting of aluminum tin alloys, aluminum titanium alloys or iron tin alloys.
  • the metal film layer has a three-dimensional porous structure in a thickness direction thereof, and the porous pore size is from 20 nm to 100 ⁇ m. Alternatively, the porous pore size is from 20 ⁇ m to 50 ⁇ m.
  • the side of the metal film layer in contact with the second surface has a three-dimensional porous structure or the metal film layer has a three-dimensional porous structure in its entire thickness direction.
  • a side of the metal film layer that is in contact with the second surface is provided with a three-dimensional porous layer having a pore size of 20 nm to 100 ⁇ m. Further optionally, the porous pore size is from 1 ⁇ m to 5 ⁇ m.
  • the three-dimensional porous layer has a thickness of from 200 nm to 300 nm.
  • the metal film layer may have a three-dimensional porous structure only at a partial position, wherein a side in contact with the second surface is provided with a three-dimensional porous layer, and the other side of the metal film layer may not have a porous structure.
  • the metal film layer may also have a three-dimensional porous structure throughout its thickness direction. Since the porous separator is a porous material, a metal film layer is deposited on the porous separator, and the metal film layer inherits the porous property of the porous separator such that a portion of the metal film layer has a porous structure or the metal film layer has a porous structure as a whole.
  • the metal film layer of the invention has a three-dimensional porous structure, which can provide an effective diffusion path for diffusion of electrons and ions, further improve the rate performance of the battery, thereby realizing rapid charge and discharge performance of ultra high magnification.
  • the metal film layer has a thickness of 0.1 ⁇ m to 300 ⁇ m, and optionally, the metal film layer has a thickness of 0.1 ⁇ m to 100 ⁇ m.
  • the separator material is not particularly limited, and an insulating porous polymer film or an inorganic porous film or the like conventionally used in the art, such as a porous polymer film, may be selected from the group consisting of a porous polypropylene film, a porous polyethylene film, and the like. Porous composite polymer film and the like.
  • the material of the porous polymer film comprises polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyoxypropylene, polyvinyl acetal, polyvinylpyrrolidone, sulfonylurea polymer.
  • polyphenylenesulfone sulfonic acid polymer polyethylene oxide, styrene butadiene rubber, polybutadiene, polyvinyl chloride, polystyrene, acrylate, chitosan,
  • the inorganic porous film may be selected from an insulating fiber paper or a porous ceramic separator, and further optionally an insulating fiber separator such as glass. Fiber diaphragms, etc.
  • the porous membrane includes a mixed layer extending from the second surface toward the inside of the porous membrane, and the metal material is adhered to the pores of the mixed layer, and the thickness of the mixed layer It is 20 nm to 10 ⁇ m, and optionally, the mixed layer has a thickness of 20 nm to 1 ⁇ m.
  • the thickness ratio of the mixed layer to the thickness of the porous separator is from 0.07% to 33.3%.
  • the thickness ratio of the mixed layer to the thickness of the porous separator is from 1.67% to 3.3%.
  • the electrolyte includes one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt;
  • the lithium salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and the like.
  • the sodium salt may be selected from the group consisting of sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, dodecyl Sodium benzenesulfonate, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, silicic acid Sodium, sodium lignosulfonate, sodium hexafluorophosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, One or more of sodium trifluo
  • the inorganic magnesium salt may be selected from Mg(ClO 4 ) 2 , Mg(BF 4 ) 2 , Mg(PF 6 ) 2 , MgCl 2 , MgBr 2 , MgF 2 , MgI 2 , Mg(NO 3 ) 2 , Mg One or more of SO 4 , Mg(SCN) 2 , MgCrO 4 , Mg(CF 3 SO 3 ) 2 ;
  • the calcium salt may be selected from the group consisting of calcium hexafluorophosphate, calcium tetrafluoroborate, calcium chloride, calcium carbonate, One or more of calcium sulfate, calcium nitrate, calcium fluoride, calcium triflate, and calcium perchlorate.
  • the concentration of the electrolyte ranges from 0.1
  • the solvent in the electrolytic solution is not particularly limited as long as the electrolyte can be dissociated into metal ions and anions, and the metal ions and anions can be freely transported.
  • the solvent may be a non-aqueous solvent or a water-based solvent, and the non-aqueous solvent may be an organic solvent or an ionic liquid, and the organic solvent is selected from one of esters, sulfones, ethers, and the like.
  • a variety of optional organic solvents may be selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), formic acid.
  • Methyl ester (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP) , ethyl acetate (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxocyclopentane (DOL), 4-methyl-1 , 3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM) , dimethyl ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crow
  • an additive in order to promote the formation of the negative electrode surface solid electrolyte membrane (SEI) to improve the structural stability, service life and performance of the negative electrode, an additive may be further added to the electrolyte, and the additive may be selected from an ester.
  • SEI negative electrode surface solid electrolyte membrane
  • One or more of a class, a sulfone, an ether, a nitrile, and an olefin Such as fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulphate, propylene sulfate, ethylene sulfate , sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, Diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoromethylethylene carbonate, three Fluoromethylethylene carbonate, vinyl chlorocarbonate, vinyl bromoacetate, trifluoroethylphosphonic
  • the integrated battery structure design proposed by the invention can also be used for conventional lithium ion batteries such as lithium manganate, lithium cobaltate, lithium titanate, lithium iron phosphate and ternary, and can also be used for storage of super capacitors, hybrid supercapacitors and the like. Energy device.
  • the first aspect of the embodiment of the present invention provides an integrated secondary battery. Since the positive current collector is directly disposed on the surface of the positive active material, so that the positive current collector and the positive active material have good contact, the contact resistance of the battery can be effectively reduced. Further, the rate performance of the battery is improved, and an ultra-high-rate secondary battery can be obtained.
  • the integrated secondary battery structure provided by the invention greatly simplifies the assembly process of the battery, and the integrated battery structure of the invention can be directly placed in the battery casing, and the electrolyte solution can be added for packaging.
  • an embodiment of the present invention further provides a method for preparing the above secondary battery, comprising the following steps:
  • the positive electrode active material is weighed in a certain ratio, and mixed well by adding a suitable solvent to form a uniform slurry; then the slurry is uniformly coated on the first surface to obtain a positive electrode active material layer, and then on the positive electrode active material layer.
  • the integrated battery body is then placed in a battery case in an inert gas or waterless environment, and the electrolyte is added and packaged to obtain an integrated secondary battery.
  • the manner of depositing includes one or more of vapor deposition, cold spray, and thermal spray, and the vapor deposition includes at least one of physical vapor deposition and chemical vapor deposition.
  • a physical vapor deposition technique may be employed, which may be selected from the group consisting of evaporation, sputtering, arc ion plating, etc., and further optionally using a sputtering technique.
  • a part of the metal material is deposited in a hole extending from the second surface toward the inside of the porous diaphragm to form the mixed layer.
  • a remaining metal material is deposited on the second surface to form the negative electrode.
  • the coating comprises one or more of knife coating, spin coating, spray coating, roll coating, and extrusion coating.
  • the embodiment of the present invention further provides a method for preparing the above secondary battery, comprising the following steps:
  • Diaphragm preparation cutting a porous polymer film or a porous organic film into a desired size, and then cleaning it for use;
  • Preparation of positive electrode active material of battery Weigh a certain proportion of positive active material, conductive agent and binder, add appropriate solvent to mechanically grind to make slurry, then uniformly apply to one side surface of the separator, and then dry it. Processing; the solvent may be selected from N-methylpyrrolidone;
  • Preparation of positive electrode current collector of battery The preparation of positive electrode current collector is carried out by vapor deposition technique. Specifically, a separator coated with a positive electrode material on one side is placed in a vapor deposition chamber, and the positive current collector source material is deposited by vapor deposition technique.
  • the positive current collector material material being a conductive material, which may be selected from aluminum, copper, iron, One of tin, zinc, nickel, manganese, titanium, lead, or the like, or an alloy containing at least one of the above metal elements, or a composite material containing at least one of the above metal elements; in the deposition process of the positive electrode current collector film, specific The masking diaphragm is not coated with the other side surface of the cathode material and the side surface of the diaphragm, so that the side surface of the diaphragm and the side surface of the diaphragm are free of film deposition; after the preparation of the cathode current collector, the surface is coated with the positive electrode active material and the positive electrode. a separator having a positive current collector film deposited on the surface of the active material is taken out from the vapor deposition chamber for use;
  • the negative electrode is prepared by vapor deposition technique, and the separator coated with the positive electrode active material on the surface and the positive electrode current collector film deposited on the surface of the positive electrode active material is placed in the vapor deposition layer.
  • the blank surface of the other side of the diaphragm is exposed to the chamber, and the anode source material is deposited on the other blank surface of the separator by a vapor deposition technique to form a film of a certain thickness to obtain a negative metal film layer.
  • the negative electrode metal film layer has a thickness of 0.1 ⁇ m to 300 ⁇ m, and the negative electrode source material is a conductor material, and may be selected from one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium, lead, or the like, or at least one An alloy of the above metal elements, or a composite material containing at least one of the above metal elements; in the deposition process of the negative electrode film, the side of the positive electrode current collector and the side surfaces of the positive electrode current collector are shielded by a specific fixture to ensure that the positive electrode set has been deposited. No film deposition on the surface and surrounding sides of the fluid film;
  • Battery assembly The above-prepared integrated structure is placed in a battery case under an inert gas or a waterless environment, and then an appropriate amount of electrolyte is added to completely infiltrate the separator, and then the package is completed.
  • steps (1) to (6) describe the operation of the secondary battery preparation method of the present invention in a specific order, it is not necessary to perform these operations in this specific order.
  • the operations of steps (1)-(5) can be performed simultaneously or in any order.
  • the preparation method of the integrated secondary battery provided by the second aspect of the embodiment of the invention is simple and easy to operate, and the preparation process of the battery can be greatly simplified.
  • Metal aluminum is used as the negative electrode active material and the negative electrode current collector
  • natural graphite is used as the positive electrode active material
  • metal aluminum is used as the positive electrode current collector
  • glass fiber paper is used as the separator
  • the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique.
  • the positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side of the glass fiber separator by magnetron sputtering technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
  • the glass fiber paper is cut into rectangular pieces of 70 mm ⁇ 140 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
  • the V-Tech MF610/610 multi-functional ion plating system was used to prepare the battery positive current collector.
  • the selected sputtering target was metal aluminum, the size was 300mm ⁇ 100mm ⁇ 10mm, and the purity was 99.5%.
  • a glass fiber paper coated with a positive electrode active material on one side was placed in a chamber of a coating system, and a side coated with a positive electrode active material was opposed to a metal aluminum target, and a distance between the target and the glass fiber paper was set to 65 mm.
  • the vacuum of the chamber is drawn to 2 ⁇ 10 -3 Pa or higher before the deposition starts.
  • the aluminum magnetron target is opened for aluminum film deposition, and the target power is set to 2.4 kW, the bias voltage is -30 V, the working pressure is 0.5 Pa, the deposition time is set to 1 hour, and the obtained positive electrode current collector is deposited.
  • the film thickness was 25 ⁇ m.
  • the glass fiber membrane is fixed in a special fixture made of stainless steel, which shields the other side surface and the peripheral side of the glass fiber paper which is not coated with the positive electrode active material, and ensures the surface during the entire deposition process. And no film deposition on the sides;
  • Battery assembly The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then in an argon atmosphere. In the protected glove box, put the wafer into the button battery case, drop the appropriate amount of electrolyte and then complete the battery assembly.
  • the aluminum-graphite secondary battery prepared in the embodiment of the present invention has a discharge specific capacity of up to 116.6 mAh/g at a rate of up to 120 C, which is discharged at a rate of 1 C. 96.7% of specific capacity (120.6 mAh/g).
  • Fig. 2(c) further demonstrates the ultrahigh rate performance and excellent coulombic efficiency of the aluminum-graphite secondary battery prepared by the embodiment of the present invention.
  • the aluminum-graphite secondary battery prepared by the embodiment of the invention has excellent cycle performance under ultra high rate conditions, as shown in FIG. 2(d), the cycle of the secondary battery at an ultrahigh magnification of 60C.
  • the number of times exceeds 1500 laps, and in the first 200 laps, the battery discharge capacity is almost 122 mAh/g without attenuation, and has a capacity retention rate close to 100%.
  • the specific capacity tends to be stable after 500 laps.
  • the embodiment of the present invention still has high cycle performance even under the condition of a magnification of up to 120 C. As shown in FIG. 3, at an ultra-high magnification of 120 C, the number of cycles of the battery can still reach 200 laps, and has a high Reversible discharge specific capacity of 102 mAh / g.
  • the positive electrode of the embodiment of the present invention exhibits ultra-high rate performance is mainly because of the unique structural design and preparation method of the secondary battery of the present invention, as shown in FIG. 4, the positive electrode of the embodiment of the present invention
  • the current collector is directly deposited on the surface of the positive electrode graphite active material.
  • the interface between the current collector and the active material has good interface contact, so that the contact resistance of the battery is lowered.
  • the negative aluminum film since the negative aluminum film is directly deposited on the surface of the glass fiber paper having a porous structure, the negative aluminum film also has a 3D porous structure, and the 3D porous structure can provide diffusion of electrons and ions. An effective path can effectively improve the rate performance of the battery.
  • the electrochemical impedance spectroscopy of the prepared integrated aluminum-graphite secondary battery was tested, and for the sake of comparison, the previous report of the team was also tested.
  • the aluminum foil is a negative electrode
  • the natural graphite is used as a positive electrode
  • the electrochemical impedance spectrum of a conventional aluminum-graphite dual ion battery using glass fiber paper as a separator is used.
  • the separators and electrolytes used in conventional aluminum-graphite dual ion batteries, including the packaging conditions are strictly consistent with the integrated aluminum-graphite secondary batteries prepared in the examples of the present invention.
  • the electrochemical impedance spectroscopy test was performed after the two batteries were cycled for 100 cycles under the condition of 2C.
  • the test results are shown in Fig. 5.
  • the integrated aluminum-graphite prepared by the embodiment of the present invention is twice.
  • the energy density and power density of the battery prepared by the embodiment of the present invention are as shown in Table 1, and compared with other commonly used energy storage devices such as lithium ion batteries, lead acid batteries, nickel hydrogen batteries and super capacitors, such as Figure 6 shows. It can be seen from FIG. 6 that the energy density and power density of the aluminum-graphite secondary battery prepared by the embodiment of the present invention are much higher than that of the conventional lithium ion battery, the lead acid battery and the nickel hydrogen battery, and have an ultra high power density comparable to that of the super capacitor. .
  • Preparation Example 1 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
  • E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material
  • E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively
  • t is the discharge time
  • Metal aluminum is used as the negative electrode active material and the negative electrode current collector
  • natural graphite is used as the positive electrode active material
  • metal aluminum is used as the positive electrode current collector
  • glass fiber paper is used as the separator
  • the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique.
  • the positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side of the glass fiber separator by thermal evaporation coating technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
  • the glass fiber paper is cut into rectangular pieces of 50 mm ⁇ 100 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
  • the vacuum positive electrode current collector was prepared by vacuum evaporation system.
  • the aluminum wire with purity of 99.9% was selected as the evaporation source material, and the aluminum wire was gasified by heating with tungsten wire.
  • a glass fiber paper coated with a positive electrode active material on one side was vertically suspended and chambered in the coating system, and the distance between the evaporation source and the glass fiber paper was set to 200 mm. In order to minimize the water and oxygen content in the deposition chamber, the vacuum of the chamber is drawn to 2 ⁇ 10 -3 Pa or higher before the deposition starts.
  • the tungsten wire heating power source is turned on, the aluminum wire is vaporized and evaporated, and the aluminum film is uniformly deposited on both surfaces of the glass fiber paper, and the deposition time is set to 1 hour, and the thickness of the deposited positive electrode current collector film and the negative electrode aluminum film is 20 ⁇ m. .
  • the fiberglass membrane is fixed in a special fixture made of stainless steel, which shields the sides of the fiberglass paper and ensures that both sides of the membrane are exposed to the coating chamber. Finally, an integrated battery body is produced;
  • Battery assembly The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then argon gas. In the atmosphere-protected glove box, the wafer is placed in a button-type battery case, an appropriate amount of electrolyte is dropped, and the battery assembly is completed.
  • the prepared secondary battery was tested for electrochemical performance using the LAND test system of Wuhan Landian Electronics Co., Ltd.
  • the test results are shown in Table 2.
  • Table 2 the aluminum-graphite secondary battery obtained by performing the positive electrode current collector and the negative electrode preparation by the evaporation coating process has an ultrahigh rate performance similar to that of the specific embodiment 1.
  • Preparation Example 2 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
  • E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material
  • E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively
  • t is the discharge time
  • Metal aluminum is used as the negative electrode active material and the negative electrode current collector
  • natural graphite is used as the positive electrode active material
  • metal aluminum is used as the positive electrode current collector
  • glass fiber paper is used as the separator
  • the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique.
  • the positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side surface of the glass fiber separator by arc ion plating technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
  • the glass fiber paper is cut into rectangular pieces of 60 mm ⁇ 120 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
  • the electrode positive current collector was prepared by arc ion plating system, and aluminum with purity of 99.5% was selected as the arc target.
  • the target diameter was 150 mm and the thickness was 20 mm.
  • a glass fiber paper coated with a positive electrode active material on one side was vertically suspended on the coating turret, and the distance between the aluminum arc target and the glass fiber paper was set to be 120 mm.
  • the vacuum of the chamber is drawn to 2 ⁇ 10 -3 Pa or higher before the deposition starts.
  • the aluminum arc target is opened to simultaneously deposit aluminum film on both surfaces of the glass fiber paper.
  • the glass fiber paper is rotated with the rotating body during the deposition process.
  • the target current was set to 60 A
  • the target voltage was 20 V
  • the bias voltage was -10 V
  • the working gas pressure was 0.8 Pa
  • the deposition time was set to 3 hours
  • the deposited positive electrode current collector film was 50 ⁇ m thick.
  • Battery assembly The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then in an argon atmosphere. In the protected glove box, put the wafer into the button battery case, drop the appropriate amount of electrolyte and then complete the battery assembly.
  • the prepared secondary battery was tested for electrochemical performance using the LAND test system of Wuhan Landian Electronics Co., Ltd.
  • the test results are shown in Table 3. It can be seen from Table 3 that the aluminum-graphite secondary battery obtained by the positive electrode current collector and the negative electrode preparation by the arc ion plating technique has a lower energy density and power density than that of the specific embodiment 1 and the specific embodiment 3. The reason is that the ion energy of the arc ion plating technology is high, which makes the structure of the negative aluminum film more dense, resulting in a decrease in porosity, but still has ultra high rate performance.
  • Preparation Example 3 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
  • E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material
  • E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively
  • t is the discharge time
  • Example 4-13 The preparation of the secondary battery of Examples 4-13 and Example 1 was the same except that the sputtering target used for preparing the battery negative electrode and the positive electrode current collector was the same, and all the other steps and materials used were the same, and Examples 4-13 were The secondary battery was tested for electrochemical performance of the battery and compared with the performance of Example 1 of the present invention.
  • the negative electrode materials used in Examples 4-13 and their electrochemical properties are detailed in Table 4.
  • the anode current collector is an aluminum film, which has high energy density and power density, and good cycle performance.
  • the positive electrode active material is natural graphite, and its energy density and power density are high.
  • Example 1 The preparation of the secondary batteries of Examples 37-43 and Example 1 was the same except that the electrolyte used to prepare the electrolyte was the same, and all the other steps and materials used were the same, while the secondary electricity of Examples 37-43 was The electrochemical performance of the cell was tested and compared with the performance of Example 1 of the present invention.
  • the positive electrode active materials used in Examples 37-43 and their electrochemical properties are detailed in Table 6.
  • the electrolyte is lithium hexafluorophosphate, which has high energy density and power density, and good cycle performance.
  • the electrolyte concentration is 4M
  • the energy density and power density are high
  • the cycle performance is good.
  • the solvent is ethyl methyl carbonate, which has high energy density and power density.
  • the type of the additive is vinylene carbonate, and the cycle performance is good.
  • the separator is glass fiber paper, which has high energy density and power density, and good cycle performance.
  • Example 78-84 All of the steps and materials used in the preparation of the secondary batteries of Examples 78-84 and Example 1 were the same except that the conductive agent, the type of the binder and the mass fraction used were different, and the same was carried out for Example 78-
  • the electrochemical performance of the secondary battery of 84 was tested and compared with the performance of Example 1 of the present invention.
  • the positive electrode active materials used in Examples 78-84 and their electrochemical properties are shown in Table 12.
  • the separator is a glass fiber paper, which has high energy density and power density, and good cycle performance.
  • the secondary battery according to the embodiment of the present invention is not limited to the button battery, and may be designed in the form of a flat battery or a cylindrical battery according to the core component.
  • the main active component of the secondary battery of the embodiment of the invention is a material for the potassium salt anion to be extracted and embedded, and the negative electrode active material is not needed in the battery system, thereby significantly reducing the battery weight and the preparation cost, and improving the energy density of the battery, and the battery It has excellent cycle stability and has broad application prospects in the field of secondary batteries.

Abstract

An integrated secondary cell, comprising an integrated main body, a cell housing, and an electrolyte solution. The integrated main body comprises a positive electrode, a porous separator membrane (02), and a negative electrode (01) sequentially arranged. The porous separator membrane (02) comprises a first surface and a second surface oppositely arranged. The positive electrode comprises a positive electrode active material layer (03) provided on the first surface, and a positive electrode current collector (04) provided on the positive electrode active material layer (03). The negative electrode (01) is provided on the second surface, and comprises a metal film layer serving as a negative electrode current collector and negative electrode active material at the same time. The electrolyte solution is filled between the positive electrode and the negative electrode (01). By directly providing the positive electrode current collector (04) on the surface of the positive electrode active material, the integrated secondary cell enables the positive electrode current collector (04) to be in good contact with the positive electrode active material, thus effectively reducing a contact resistance of the cell, and accordingly improving the rate capability thereof. In addition, the integrated secondary cell has a simple structure. Also provided is a manufacturing method of the integrated secondary cell.

Description

一种一体化二次电池及其制备方法Integrated secondary battery and preparation method thereof 技术领域Technical field
本发明涉及二次电池技术领域，特别是涉及一种一体化二次电池及其制备方法。The present invention relates to the field of secondary battery technology, and in particular to an integrated secondary battery and a method of fabricating the same.
背景技术Background technique
锂离子二次电池具有工作电压高、能量和功率密度大、重量轻、寿命长、无记忆效应、自放电效应低等优点，已广泛应用于各种电子设备，如手机、数码相机、笔记本电脑、电动工具、无人机、电动汽车等。近年来，随着电动工具、车模、航模、船模、无人机、电动汽车等产业的快速发展，对锂离子电池的性能要求越来越高。因为，这些设备不仅要求锂离子电池具有高的能量密度和使用寿命，而且要求锂离子电池满足大电流充放电的高倍率性能。而一般商用锂离子电池倍率性能较差，通常仅可以达到3C，导致充放电时间长，大电流放电性能差，设备无法实现瞬间或持续的高功率输出；而且大电流放电会导致电池内部温度短时间急剧升高，存在热失控的安全风险，将造成电池使用寿命锐减。Lithium ion secondary batteries have the advantages of high operating voltage, high energy and power density, light weight, long life, no memory effect, low self-discharge effect, etc., and have been widely used in various electronic devices, such as mobile phones, digital cameras, notebook computers. , power tools, drones, electric cars, etc. In recent years, with the rapid development of power tools, car models, aircraft models, ship models, drones, electric vehicles and other industries, the performance requirements for lithium-ion batteries are getting higher and higher. Because these devices not only require high energy density and longevity of lithium ion batteries, but also require lithium ion batteries to meet the high rate performance of high current charge and discharge. The general commercial lithium-ion battery has poor rate performance, usually only reaches 3C, resulting in long charging and discharging time, poor current discharge performance, and equipment can not achieve instantaneous or continuous high power output; and large current discharge will cause the battery internal temperature to be short. The sharp increase in time and the risk of thermal runaway safety will result in a sharp drop in battery life.
锂离子电池低的倍率性能主要是充放电过程中低的电子和离子传输速度造成的，为了解决这一问题，研究人员尝试了多种方法，如：设计具有高的离子扩散系数的活性材料、采用纳米材料缩短电子和离子的扩散距离、构建三维网络结构为电子和离子的扩散提供有效路径，以及添加导电剂(石墨烯、碳纳米管等)和包覆导电层(通常为碳层)等等。虽然这些方法可以提高电极材料的倍率性能，但是由于电池结构以及制备工艺的限制，还是难以使全电池实现超高倍率性能。The low rate performance of lithium-ion batteries is mainly caused by low electron and ion transport speeds during charge and discharge. To solve this problem, researchers have tried various methods, such as designing active materials with high ion diffusion coefficients. Use nanomaterials to shorten the diffusion distance of electrons and ions, construct a three-dimensional network structure to provide an effective path for the diffusion of electrons and ions, and add conductive agents (graphene, carbon nanotubes, etc.) and coated conductive layers (usually carbon layers). Wait. Although these methods can improve the rate performance of the electrode material, it is difficult to achieve ultra-high rate performance of the full battery due to limitations in the structure of the battery and the manufacturing process.
发明内容Summary of the invention
鉴于此，本发明提供了一种一体化二次电池，该电池中，由于正极集流体直接设置在正极活性材料表面，使得正极集流体与正极活性材料之间具有良好的 接触，可以有效降低电池的接触电阻，进而提高电池的倍率性能。In view of this, the present invention provides an integrated secondary battery in which a positive electrode current collector is directly disposed on a surface of a positive electrode active material, so that a positive electrode current collector and a positive electrode active material have a good relationship between them. Contact can effectively reduce the contact resistance of the battery, thereby improving the rate performance of the battery.
具体地，第一方面，本发明提供了一种一体化二次电池，包括一体化电池主体、电池壳体和电解液，所述一体化电池主体包括依次设置的正极、多孔隔膜和负极；所述多孔隔膜包括相对设置的第一表面和第二表面；所述正极包括设置在所述第一表面上的正极活性材料层和设置在所述正极活性材料层上的正极集流体；所述负极设置在所述第二表面上，所述负极包括金属膜层，所述金属膜层同时作为负极集流体和负极活性材料；所述电解液填充于所述正极与所述负极之间。Specifically, in a first aspect, the present invention provides an integrated secondary battery including an integrated battery body, a battery case, and an electrolyte, the integrated battery body including a positive electrode, a porous separator, and a negative electrode disposed in sequence; The porous separator includes opposite first and second surfaces; the positive electrode includes a positive active material layer disposed on the first surface and a positive current collector disposed on the positive active material layer; Provided on the second surface, the negative electrode includes a metal film layer simultaneously serving as a negative electrode current collector and a negative electrode active material; the electrolyte solution is filled between the positive electrode and the negative electrode.
其中，所述金属膜层通过沉积的方式设置在所述第二表面上。Wherein the metal film layer is disposed on the second surface by deposition.
其中，所述正极活性材料层通过涂覆的方式设置在所述第一表面上；所述正极集流体通过沉积的方式设置在所述正极活性材料层上。Wherein the positive active material layer is disposed on the first surface by coating; the positive current collector is disposed on the positive active material layer by deposition.
其中，所述金属膜层在其厚度方向上具有三维多孔结构，多孔孔径大小为20nm-100μm。Wherein, the metal film layer has a three-dimensional porous structure in a thickness direction thereof, and the porous pore size is from 20 nm to 100 μm.
其中，所述金属膜层的材质为金属材料，所述金属材料包括铝、铜、铁、锡、锌、镍、锰、钛和铅中的任意一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料。Wherein, the material of the metal film layer is a metal material, and the metal material comprises any one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium and lead, or contains at least one of the above metal elements. An alloy, or a composite material containing at least one of the above metal elements.
其中，所述多孔隔膜包括一自所述第二表面向所述多孔隔膜内部延伸形成的混合层，所述混合层的孔洞中附着有所述金属材料，所述混合层的厚度为20nm-10μm。Wherein, the porous membrane comprises a mixed layer extending from the second surface toward the inside of the porous membrane, and the metal material is adhered to the pores of the mixed layer, and the mixed layer has a thickness of 20 nm to 10 μm. .
其中，所述金属膜层的厚度为0.1μm-300μm。Wherein, the thickness of the metal film layer is from 0.1 μm to 300 μm.
其中，所述正极集流体的厚度为0.1μm-300μm，所述正极活性材料层的厚度为10μm-100μm。The positive electrode current collector has a thickness of 0.1 μm to 300 μm, and the positive electrode active material layer has a thickness of 10 μm to 100 μm.
其中，所述正极活性材料包括碳材料、硫化物、氮化物、氧化物、碳化物、以及上述各材料的复合物中的一种或多种。Wherein, the positive electrode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials.
其中，所述电解液包括电解质和溶剂，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；所述电解液中，所述电解质的浓度为0.1-10mol/L。Wherein the electrolyte comprises an electrolyte and a solvent, the electrolyte comprising one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt and a calcium salt; wherein the electrolyte has a concentration of 0.1- 10 mol / L.
本发明第一方面提供的一体化二次电池，由于正极集流体直接设置在正极活性材料表面上，使得正极集流体与正极活性材料之间具有良好的接触，可以有 效降低电池的接触电阻，进而提高电池的倍率性能；本发明的一体化二次电池结构简单，可以大大简化电池的组装工艺，只需将本发明所述一体化电池结构直接置于电池壳体中，加入电解液进行封装即可，简单方便。In the integrated secondary battery provided by the first aspect of the present invention, since the positive electrode current collector is directly disposed on the surface of the positive electrode active material, the positive electrode current collector and the positive electrode active material have good contact, and there may be The utility model reduces the contact resistance of the battery, thereby improving the rate performance of the battery; the integrated secondary battery of the invention has a simple structure, can greatly simplify the assembly process of the battery, and only needs to directly place the integrated battery structure of the invention in the battery casing In addition, the electrolyte can be added for packaging, which is simple and convenient.
本发明实施方式第二方面提供了一种一体化二次电池的制备方法，包括以下步骤：A second aspect of the embodiments of the present invention provides a method for preparing an integrated secondary battery, comprising the following steps:
提供多孔隔膜，所述多孔隔膜包括相对设置的第一表面和第二表面；Providing a porous membrane comprising opposing first and second surfaces;
按一定比例称取正极活性材料，加入适当溶剂充分混合形成均匀浆料；然后将所述浆料均匀涂覆于所述第一表面，得到正极活性材料层，然后在所述正极活性材料层上通过沉积的方式制备正极集流体，形成正极；The positive electrode active material is weighed in a certain ratio, and mixed well by adding a suitable solvent to form a uniform slurry; then the slurry is uniformly coated on the first surface to obtain a positive electrode active material layer, and then on the positive electrode active material layer. Preparing a positive electrode current collector by deposition to form a positive electrode;
在所述第二表面上沉积金属材料形成金属膜层，得到负极；最终得到一体化电池主体；Depositing a metal material on the second surface to form a metal film layer to obtain a negative electrode; finally obtaining an integrated battery body;
在惰性气体或无水环境下，然后将所述一体化电池主体装入电池壳体中，加入电解液后封装，得到一体化二次电池。The integrated battery body is then placed in a battery case in an inert gas or waterless environment, and the electrolyte is added and packaged to obtain an integrated secondary battery.
其中，所述沉积的方式包括气相沉积、冷喷涂和热喷涂的中一种或多种，所述气相沉积包括物理气相沉积和化学气相沉积中的至少一种。Wherein, the manner of depositing includes one or more of vapor deposition, cold spray, and thermal spray, and the vapor deposition includes at least one of physical vapor deposition and chemical vapor deposition.
其中，所述涂覆的方式包括刮涂、旋涂、喷涂、滚涂和挤压涂布中的一种或多种。Wherein, the coating method comprises one or more of knife coating, spin coating, spray coating, roll coating and extrusion coating.
本发明第二方面提供的二次电池的制备方法，工艺简单，适于规模化生产。The method for preparing a secondary battery provided by the second aspect of the invention has a simple process and is suitable for large-scale production.
附图说明DRAWINGS
图1为本发明实施例提供的一体化二次电池的结构示意图；1 is a schematic structural view of an integrated secondary battery according to an embodiment of the present invention;
图2为本发明实施例1所制备一体化铝-石墨双离子电池在1、10、30C倍率下的充放电曲线(a)，及在60、90、120C倍率下的充放电曲线(b)，1-120C倍率下二次电池的倍率性能及相应的库伦效率(c)，在60C倍率条件下的循环1500圈的循环性能曲线(d)；2 is a charge-discharge curve (a) of an integrated aluminum-graphite dual ion battery prepared according to Example 1 of the present invention at a ratio of 1, 10, and 30 C, and a charge-discharge curve at a rate of 60, 90, and 120 C (b). , the rate performance of the secondary battery at a ratio of 1-120C and the corresponding coulombic efficiency (c), the cycle performance curve of the cycle of 1500 cycles at 60C rate (d);
图3为本发明实施例1所制备的铝-石墨二次电池在120C的超高倍率下循环200圈的循环性能曲线；3 is a cycle performance curve of an aluminum-graphite secondary battery prepared in Example 1 of the present invention at a super high rate of 120 C for 200 cycles;
图4为本发明实施例1所制备铝-石墨二次电池的扫描电镜图，(a)电池负极 与多孔隔膜界面处负极铝膜层的多孔结构形貌,(b)电池正极集流体铝膜层与正极石墨活性材料的界面结合形貌；4 is a scanning electron micrograph of an aluminum-graphite secondary battery prepared in Example 1 of the present invention, (a) a battery negative electrode The porous structure of the negative aluminum film layer at the interface with the porous membrane, (b) the interface morphology of the positive electrode current collector aluminum film layer and the positive electrode graphite active material;
图5为本发明实施例1所制备铝-石墨二次电池(圆圈)和常规铝-石墨双离子电池(圆点)的电化学阻抗谱；5 is an electrochemical impedance spectroscopy spectrum of an aluminum-graphite secondary battery (circle) and a conventional aluminum-graphite dual ion battery (dot) prepared in Example 1 of the present invention;
图6为本发明实施例1所制备铝-石墨二次电池与其它常用储能器件(锂离子电池、铅酸电池、镍氢电池以及超级电容器)的能量密度和功率密度比较图。6 is a comparison diagram of energy density and power density of an aluminum-graphite secondary battery and a conventional energy storage device (a lithium ion battery, a lead acid battery, a nickel hydrogen battery, and a super capacitor) prepared in Example 1 of the present invention.
具体实施方式detailed description
下面结合附图和具体实施方式对本发明作进一步详细说明。以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。The present invention will be further described in detail below in conjunction with the drawings and specific embodiments. The following are the preferred embodiments of the embodiments of the present invention, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.
参照图1，图1中01代表负极、02代表多孔隔膜、03代表正极活性材料层、04代表正极集流体。本发明实施例第一方面提供了一种一体化二次电池，包括一体化电池主体、电池壳体和电解液，所述一体化电池主体包括依次设置的正极、多孔隔膜和负极；所述多孔隔膜包括相对设置的第一表面和第二表面；所述正极包括设置在所述第一表面上的正极活性材料层和设置在所述正极活性材料层上的正极集流体；所述负极设置在所述第二表面上，所述负极包括金属膜层，所述金属膜层同时作为负极集流体和负极活性材料；所述电解液填充于所述正极与所述负极之间。Referring to Fig. 1, in Fig. 1, 01 represents a negative electrode, 02 represents a porous separator, 03 represents a positive electrode active material layer, and 04 represents a positive electrode current collector. A first aspect of an embodiment of the present invention provides an integrated secondary battery including an integrated battery body, a battery case, and an electrolyte, wherein the integrated battery body includes a positive electrode, a porous separator, and a negative electrode disposed in sequence; The separator includes a first surface and a second surface disposed opposite to each other; the positive electrode includes a positive active material layer disposed on the first surface and a positive current collector disposed on the positive active material layer; the negative electrode is disposed at On the second surface, the negative electrode includes a metal film layer serving as a negative electrode current collector and a negative electrode active material at the same time; the electrolyte solution is filled between the positive electrode and the negative electrode.
本发明实施方式中，所述正极活性材料具有层状晶体结构。In an embodiment of the invention, the cathode active material has a layered crystal structure.
本发明实施方式中，所述正极活性材料包括碳材料、硫化物、氮化物、氧化物、碳化物、以及上述各材料的复合物中的一种或多种。其中，所述碳材料包括石墨类碳材料、玻璃碳、碳碳复合材料、碳纤维、硬碳、多孔炭、炭黑、碳纳米管、石墨烯中的一种或多种。具体地，所述石墨类碳材料包括天然石墨、膨胀石墨、人造石墨、鳞片石墨、球形石墨、中间相碳微球石墨、热解石墨、高取向石墨、三维石墨海绵中的一种或多种。In an embodiment of the invention, the cathode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials. Wherein, the carbon material comprises one or more of a graphite-based carbon material, a glassy carbon, a carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotubes, and graphene. Specifically, the graphite-based carbon material includes one or more of natural graphite, expanded graphite, artificial graphite, flake graphite, spherical graphite, mesocarbon microbead graphite, pyrolytic graphite, high-orientation graphite, and three-dimensional graphite sponge. .
本发明实施方式中，所述硫化物选自二硫化钼、二硫化钨、二硫化钒、二硫 化钛、二硫化铁、硫化亚铁、硫化镍、硫化锌、硫化钴、硫化锰中的一种或多种；所述氮化物选自六方氮化硼、碳掺杂六方氮化硼中的一种或多种；所述氧化物选自三氧化钼、三氧化钨、五氧化二钒、二氧化钒、二氧化钛、氧化锌、氧化铜、氧化镍、氧化锰中的一种或多种；所述碳化物选自碳化钛、碳化钽、碳化钼、碳化硅中的一种或多种。In an embodiment of the invention, the sulfide is selected from the group consisting of molybdenum disulfide, tungsten disulfide, vanadium disulfide, and disulfide. One or more of titanium, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, manganese sulfide; the nitride is selected from the group consisting of hexagonal boron nitride and carbon doped hexagonal boron nitride One or more; the oxide is one or more selected from the group consisting of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, and manganese oxide; The carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide, and silicon carbide.
本发明实施方式中，正极活性材料层还包括导电剂以及粘结剂，所述正极活性材料与导电剂和粘结剂的配比无特别限制，采用本领域现有常规配比即可，如正极活性材料的质量含量为60％-90％，导电剂的质量含量为0.1％-30％，粘结剂的质量含量为0.5％-15％。对导电剂没有特别限制，采用本领域现有常规材料即可，如导电炭黑、导电乙炔黑、Super P导电碳球、导电石墨KS6、碳纳米管、石墨烯等一种或多种。所述正极活性材料层中加入的粘结剂也没有特殊限制，采用本领域现有常规材料即可，如聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃等的一种或多种。In the embodiment of the present invention, the positive electrode active material layer further includes a conductive agent and a binder, and the ratio of the positive electrode active material to the conductive agent and the binder is not particularly limited, and the conventional ratio in the art may be used, such as The positive electrode active material has a mass content of 60% to 90%, the conductive agent has a mass content of 0.1% to 30%, and the binder has a mass content of 0.5% to 15%. The conductive agent is not particularly limited, and may be one or more of conventional materials available in the art, such as conductive carbon black, conductive acetylene black, Super P conductive carbon sphere, conductive graphite KS6, carbon nanotube, graphene, and the like. The binder to be added to the positive electrode active material layer is also not particularly limited, and conventional materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and SBR rubber may be used. One or more of polyolefins, and the like.
本发明实施方式中，所述正极活性材料层通过涂覆的方式设置在所述第一表面上；所述涂覆的方式包括刮涂、旋涂、喷涂、滚涂和挤压涂布中的一种或多种。In an embodiment of the present invention, the positive electrode active material layer is disposed on the first surface by coating; the coating manner includes blade coating, spin coating, spray coating, roll coating, and extrusion coating. One or more.
本发明实施方式中，所述正极集流体通过沉积的方式设置于正极活性材料表面。所述沉积正极集流体所用的沉积技术可以选自物理气相沉积技术和化学气相沉积技术中的至少一种，以及冷喷涂技术和热喷涂技术等的一种或多种的复合；本发明可选的采用物理气相沉积技术，可以选自蒸发、溅射、电弧离子镀等，进一步可选的采用溅射技术。本发明采用沉积技术制得的正极集流体为膜材料，具有良好的柔韧性，可以用于制备成柔性二次电池。In an embodiment of the invention, the cathode current collector is disposed on the surface of the cathode active material by deposition. The deposition technique used for depositing the cathode current collector may be selected from at least one of a physical vapor deposition technique and a chemical vapor deposition technique, and a composite of one or more of a cold spray technique and a thermal spray technique; The physical vapor deposition technique can be selected from the group consisting of evaporation, sputtering, arc ion plating, etc., and further optionally using sputtering technology. The positive electrode current collector prepared by the deposition technique is a film material, has good flexibility, and can be used for preparing a flexible secondary battery.
本发明实施方式中，所述正极集流体的材质包括铝、铜、铁、锡、锌、镍、钛、锰和铅中的任意一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料。In the embodiment of the present invention, the material of the cathode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, and lead, or an alloy containing at least one of the above metal elements, or contains a composite material of at least one of the above metal elements.
本发明实施方式中，所述正极活性材料层的厚度为10μm-100μm；所述正极集流体的厚度为0.1μm-300μm，可选地，正极集流体的厚度为0.1μm-100μm。 In an embodiment of the invention, the thickness of the positive electrode active material layer is from 10 μm to 100 μm; the thickness of the positive electrode current collector is from 0.1 μm to 300 μm, and optionally, the thickness of the positive electrode current collector is from 0.1 μm to 100 μm.
本发明实施方式中，所述金属膜层通过沉积的方式设置在所述第二表面上。本发明采用沉积技术制得的金属膜层为膜材料，具有良好的柔韧性，可以用于制备成柔性二次电池。In an embodiment of the invention, the metal film layer is disposed on the second surface by deposition. The metal film layer prepared by the deposition technology of the invention is a film material, has good flexibility, and can be used for preparing a flexible secondary battery.
本发明实施方式中，所述金属膜层的材质为金属材料，所述金属材料包括铝、铜、铁、锡、锌、镍、锰、钛和铅中的任意一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料。可选地，所述合金可选自铝锡合金、铝钛合金或铁锡合金。In the embodiment of the present invention, the material of the metal film layer is a metal material, and the metal material includes any one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium, and lead, or contains at least one kind of An alloy of the above metal elements or a composite material containing at least one of the above metal elements. Alternatively, the alloy may be selected from the group consisting of aluminum tin alloys, aluminum titanium alloys or iron tin alloys.
本发明一实施方式中，所述金属膜层在其厚度方向上具有三维多孔结构，多孔孔径大小为20nm-100μm。可选地，多孔孔径大小为20μm-50μm。可选地，所述金属膜层与所述第二表面接触的一侧具有三维多孔结构或所述金属膜层在其整个厚度方向上均具有三维多孔结构。可选地，所述金属膜层中与所述第二表面接触的一侧设有三维多孔层，多孔孔径大小为20nm-100μm。进一步可选地，多孔孔径大小为1μm-5μm。所述三维多孔层的厚度为200nm-300nm。该实施例中，金属膜层中可仅部分位置具有三维多孔结构，其中是与第二表面接触的一侧设有三维多孔层，金属膜层的另一侧可不具有多孔结构。金属膜层也可以在其整个厚度方向上均具有三维多孔结构。由于多孔隔膜为多孔材料，在所述多孔隔膜上沉积制备金属膜层，金属膜层会继承多孔隔膜的多孔性质从而金属膜层中部分位置具有多孔结构或者金属膜层整体具有多孔结构。In one embodiment of the invention, the metal film layer has a three-dimensional porous structure in a thickness direction thereof, and the porous pore size is from 20 nm to 100 μm. Alternatively, the porous pore size is from 20 μm to 50 μm. Optionally, the side of the metal film layer in contact with the second surface has a three-dimensional porous structure or the metal film layer has a three-dimensional porous structure in its entire thickness direction. Optionally, a side of the metal film layer that is in contact with the second surface is provided with a three-dimensional porous layer having a pore size of 20 nm to 100 μm. Further optionally, the porous pore size is from 1 μm to 5 μm. The three-dimensional porous layer has a thickness of from 200 nm to 300 nm. In this embodiment, the metal film layer may have a three-dimensional porous structure only at a partial position, wherein a side in contact with the second surface is provided with a three-dimensional porous layer, and the other side of the metal film layer may not have a porous structure. The metal film layer may also have a three-dimensional porous structure throughout its thickness direction. Since the porous separator is a porous material, a metal film layer is deposited on the porous separator, and the metal film layer inherits the porous property of the porous separator such that a portion of the metal film layer has a porous structure or the metal film layer has a porous structure as a whole.
本发明中金属膜层具有三维多孔结构可为电子和离子的扩散提供有效的扩散路径，进一步提高电池的倍率性能，从而实现超高倍率的快速充放电性能。The metal film layer of the invention has a three-dimensional porous structure, which can provide an effective diffusion path for diffusion of electrons and ions, further improve the rate performance of the battery, thereby realizing rapid charge and discharge performance of ultra high magnification.
本发明实施方式中，所述金属膜层的厚度为0.1μm-300μm，可选地，所述金属膜层的厚度为0.1μm-100μm。In an embodiment of the invention, the metal film layer has a thickness of 0.1 μm to 300 μm, and optionally, the metal film layer has a thickness of 0.1 μm to 100 μm.
本发明实施方式中，所述隔膜材料无特别限制，采用本领域常规使用的绝缘的多孔聚合物薄膜或无机多孔薄膜等，如多孔聚合物薄膜可选自多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜等。具体地，所述多孔聚合物薄膜的材质包括聚氧化乙烯、聚甲基丙烯酸甲酯、聚偏氟乙烯-六氟丙烯、聚氧丙烯、聚乙烯醇缩醛、聚乙烯吡咯烷酮、磺脲聚合物、聚亚苯基砜磺酸聚合物、聚环氧乙烷、丁苯橡胶、聚丁二烯、聚氯乙烯、聚苯乙烯、丙烯酸酯、壳糖酸、 聚乙烯醇、聚乙烯醇缩丁醛、聚乙二醇、聚醚丙烯酸乙二醇酯、聚乙烯、聚丙烯、磷酸酯类聚合物中的一种或多种，或上述任意一种或几种聚合物的共混、共聚、接枝、梳化、超支化或交联网络物；无机多孔薄膜可选自绝缘纤维纸或多孔陶瓷隔膜等，进一步可选地的采用绝缘纤维隔膜，如玻璃纤维隔膜等。In the embodiment of the present invention, the separator material is not particularly limited, and an insulating porous polymer film or an inorganic porous film or the like conventionally used in the art, such as a porous polymer film, may be selected from the group consisting of a porous polypropylene film, a porous polyethylene film, and the like. Porous composite polymer film and the like. Specifically, the material of the porous polymer film comprises polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyoxypropylene, polyvinyl acetal, polyvinylpyrrolidone, sulfonylurea polymer. , polyphenylenesulfone sulfonic acid polymer, polyethylene oxide, styrene butadiene rubber, polybutadiene, polyvinyl chloride, polystyrene, acrylate, chitosan, One or more of polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyether acrylate, polyethylene, polypropylene, phosphate polymer, or any one or more of the above a polymer blending, copolymerization, grafting, combing, hyperbranched or crosslinked network; the inorganic porous film may be selected from an insulating fiber paper or a porous ceramic separator, and further optionally an insulating fiber separator such as glass. Fiber diaphragms, etc.
本发明实施方式中，所述多孔隔膜包括一自所述第二表面向所述多孔隔膜内部延伸形成的混合层，所述混合层的孔洞中附着有所述金属材料，所述混合层的厚度为20nm-10μm，可选地，所述混合层的厚度为20nm-1μm。所述混合层的厚度与所述多孔隔膜的厚度比为0.07％-33.3％。可选地，所述混合层的厚度与所述多孔隔膜的厚度比为1.67％-3.3％。In an embodiment of the present invention, the porous membrane includes a mixed layer extending from the second surface toward the inside of the porous membrane, and the metal material is adhered to the pores of the mixed layer, and the thickness of the mixed layer It is 20 nm to 10 μm, and optionally, the mixed layer has a thickness of 20 nm to 1 μm. The thickness ratio of the mixed layer to the thickness of the porous separator is from 0.07% to 33.3%. Optionally, the thickness ratio of the mixed layer to the thickness of the porous separator is from 1.67% to 3.3%.
本发明实施方式中，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；锂盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂等的一种或多种，进一步可选为六氟磷酸锂；钠盐可选自氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠(NaTFSI)、LiCF3SO3、LiN(SO2CF3)2中的一种或多种，进一步可选为六氟磷酸钠；钾盐可选自氯化钾、氟化钾、硫酸钾、碳酸钾、磷酸钾、硝酸钾、二氟草酸硼酸钾、焦磷酸钾、十二烷基苯磺酸钾、十二烷基硫酸钾、柠檬酸三钾、偏硼酸钾、硼酸钾、钼酸钾、钨酸钾、溴化钾、亚硝酸钾、碘酸钾、碘化钾、硅酸钾、木质素磺酸钾、草酸钾、铝酸钾、甲基磺酸钾、醋酸钾、重铬酸钾、六氟砷酸钾、四氟硼酸钾、高氯酸钾、三氟甲烷磺酰亚胺钾(KTFSI)、KCF3SO3、KN(SO2CF3)2中的一种或多种，进一步可选为六氟磷酸钾；镁盐可以选自有机镁盐或无机镁盐，其中有机镁盐可以选用格氏试剂RMgX，包括但不限于N-甲基苯胺溴化镁、吡咯基溴化镁、乙二胺四乙酸二钠镁(EDTA-Mg)、N,N-二(三甲基硅基)氨基氯化镁、Mg(SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2型配合物中的一种或多种，其中，R为烷基，X为卤素，A为Al、B、As、P、Sb、Ta或Fe，Z为Cl或Br，R'为芳基，且n'+n”＝n，其中无机镁盐可以选自 Mg(ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2中的一种或多种；钙盐可以选自六氟磷酸钙、四氟硼酸钙、氯化钙、碳酸钙、硫酸钙、硝酸钙、氟化钙、三氟甲磺酸钙、高氯酸钙中的一种或多种。所述电解液中，所述电解质的浓度范围为0.1-10mol/L。In an embodiment of the invention, the electrolyte includes one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt; the lithium salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and the like. One or more, further selected from lithium hexafluorophosphate; the sodium salt may be selected from the group consisting of sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, dodecyl Sodium benzenesulfonate, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, silicic acid Sodium, sodium lignosulfonate, sodium hexafluorophosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, One or more of sodium trifluoromethanesulfonimide (NaTFSI), LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , further optionally sodium hexafluorophosphate; potassium salt may be selected from potassium chloride , potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalate borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, dodecyl sulfur Potassium acid, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, Potassium aluminate, potassium methanesulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide (KTFSI), KCF 3 SO 3 , KN One or more of (SO 2 CF 3 ) 2 may further be selected from potassium hexafluorophosphate; the magnesium salt may be selected from the group consisting of an organic magnesium salt or an inorganic magnesium salt, wherein the organic magnesium salt may be selected from the Grignard reagent RMgX, including but Not limited to N-methylaniline magnesium bromide, pyrrolyl magnesium bromide, disodium magnesium edetate (EDTA-Mg), N,N-bis(trimethylsilyl)aminomagnesium chloride, Mg (SnPh 3 2 , one or more of Mg(BR 2 R' 2 ) 2 , Mg(AZ 3-n R n' R'n" ) type 2 complexes, wherein R is an alkyl group and X is a halogen. A is Al, B, As, P, Sb, Ta or Fe, Z is Cl or Br, R' is an aryl group, and n'+n"=n, wherein the inorganic magnesium salt may be selected from Mg(ClO 4 ) 2 , Mg(BF 4 ) 2 , Mg(PF 6 ) 2 , MgCl 2 , MgBr 2 , MgF 2 , MgI 2 , Mg(NO 3 ) 2 , Mg One or more of SO 4 , Mg(SCN) 2 , MgCrO 4 , Mg(CF 3 SO 3 ) 2 ; the calcium salt may be selected from the group consisting of calcium hexafluorophosphate, calcium tetrafluoroborate, calcium chloride, calcium carbonate, One or more of calcium sulfate, calcium nitrate, calcium fluoride, calcium triflate, and calcium perchlorate. In the electrolytic solution, the concentration of the electrolyte ranges from 0.1 to 10 mol/L.
本发明实施方式中，对电解液中的溶剂没有特别限制，只要可以使电解质离解成金属离子和阴离子，且金属离子和阴离子可以自由迁移即可。具体地，所述溶剂可以为非水基溶剂或水基溶剂，所述非水基溶剂可以为有机溶剂或离子液体，所述有机溶剂选自酯类、砜类、醚类等的一种或多种，可选的有机溶剂可选自碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(12-冠-4)中的一种或多种，进一步可选为碳酸甲乙酯；所述离子液体可选自1-乙基-3-甲基咪唑-六氟磷酸盐、1-乙基-3-甲基咪唑-四氟硼酸盐、1-乙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丙基-3-甲基咪唑-六氟磷酸盐、1-丙基-3-甲基咪唑-四氟硼酸盐、1-丙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基咪唑-六氟磷酸盐、1-丁基-1-甲基咪唑-四氟硼酸盐、1-丁基-1-甲基咪唑-双三氟甲基磺酰亚胺盐、N-丁基-N-甲基吡咯烷-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲基-N-丙基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲,丙基哌啶-双三氟甲基磺酰亚胺盐、N-甲,丁基哌啶-双三氟甲基磺酰亚胺盐中的一种或多种。In the embodiment of the present invention, the solvent in the electrolytic solution is not particularly limited as long as the electrolyte can be dissociated into metal ions and anions, and the metal ions and anions can be freely transported. Specifically, the solvent may be a non-aqueous solvent or a water-based solvent, and the non-aqueous solvent may be an organic solvent or an ionic liquid, and the organic solvent is selected from one of esters, sulfones, ethers, and the like. A variety of optional organic solvents may be selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), formic acid. Methyl ester (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP) , ethyl acetate (EA), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxocyclopentane (DOL), 4-methyl-1 , 3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM) , dimethyl ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4 And one or more, further optionally ethyl methyl carbonate; the ionic liquid may be selected from the group consisting of 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-B -3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-propyl-3-methylimidazolium-hexafluorophosphate , 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylimidazole - hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonimide salt, N-butyl- N-methylpyrrolidine-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonimide salt, N-methyl-N-propyl Pyrrolidine-bistrifluoromethylsulfonimide salt, N-methyl, propyl piperidine-bistrifluoromethylsulfonimide salt, N-methyl, butyl piperidine-bistrifluoromethylsulfonyl One or more of the imine salts.
本发明实施方式中，为了促进负极表面固体电解质膜(SEI)的形成，以提高负极的结构稳定性、使用寿命和性能，可以进一步在所述电解液中加入添加剂，所述添加剂可以选自酯类、砜类、醚类、腈类和烯烃类等的一种或多种， 如氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂、二甲基亚砜、苯甲醚、乙酰胺、二氮杂苯、间二氮杂苯、冠醚12-冠-4、冠醚18-冠-6、4-氟苯甲醚、氟代链状醚、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、溴代碳酸乙烯酯、三氟乙基膦酸、溴代丁内酯、氟代乙酸基乙烷、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、二氧化碳、二氧化硫、碳酸锂中的一种或多种，进一步可选为碳酸亚乙烯酯(VC)，所述添加剂在所述电解液中的质量分数为0.1％-40％，进一步可选的为1％-6％。In the embodiment of the present invention, in order to promote the formation of the negative electrode surface solid electrolyte membrane (SEI) to improve the structural stability, service life and performance of the negative electrode, an additive may be further added to the electrolyte, and the additive may be selected from an ester. One or more of a class, a sulfone, an ether, a nitrile, and an olefin, Such as fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulphate, propylene sulfate, ethylene sulfate , sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, Diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoromethylethylene carbonate, three Fluoromethylethylene carbonate, vinyl chlorocarbonate, vinyl bromoacetate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phosphite, phosphazene, Ethanolamine, dimethylamine, cyclobutylsulfone, 1,3-dioxocyclopentane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, cerium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, carbonic acid One or more of lithium, further optionally vinylene carbonate (VC), the additive having a mass fraction in the electrolyte of 0.1% to 40%, further Optional is 1% - 6%.
本发明所提出的一体化电池结构设计还可以用于锰酸锂、钴酸锂、钛酸锂、磷酸铁锂以及三元等常规锂离子电池，还可以用于超级电容器、混合超级电容器等储能器件。The integrated battery structure design proposed by the invention can also be used for conventional lithium ion batteries such as lithium manganate, lithium cobaltate, lithium titanate, lithium iron phosphate and ternary, and can also be used for storage of super capacitors, hybrid supercapacitors and the like. Energy device.
本发明实施例第一方面提供了一体化二次电池，由于正极集流体直接设置在正极活性材料的表面，使得正极集流体与正极活性材料之间具有良好的接触，可以有效降低电池的接触电阻，进而提高电池的倍率性能，可得到超高倍率二次电池。本发明提供的一体化二次电池结构大大简化电池的组装工艺，只需将本发明所述一体化电池结构直接置于电池壳体中，加入电解液进行封装即可。The first aspect of the embodiment of the present invention provides an integrated secondary battery. Since the positive current collector is directly disposed on the surface of the positive active material, so that the positive current collector and the positive active material have good contact, the contact resistance of the battery can be effectively reduced. Further, the rate performance of the battery is improved, and an ultra-high-rate secondary battery can be obtained. The integrated secondary battery structure provided by the invention greatly simplifies the assembly process of the battery, and the integrated battery structure of the invention can be directly placed in the battery casing, and the electrolyte solution can be added for packaging.
相应地，本发明实施例还提供了一种上述二次电池的制备方法，包括以下步骤：Correspondingly, an embodiment of the present invention further provides a method for preparing the above secondary battery, comprising the following steps:
提供多孔隔膜，所述多孔隔膜包括相对设置的第一表面和第二表面；Providing a porous membrane comprising opposing first and second surfaces;
按一定比例称取正极活性材料，加入适当溶剂充分混合形成均匀浆料；然后将所述浆料均匀涂覆于所述第一表面，得到正极活性材料层，然后在所述正极活性材料层上通过沉积的方式制备正极集流体，形成正极；The positive electrode active material is weighed in a certain ratio, and mixed well by adding a suitable solvent to form a uniform slurry; then the slurry is uniformly coated on the first surface to obtain a positive electrode active material layer, and then on the positive electrode active material layer. Preparing a positive electrode current collector by deposition to form a positive electrode;
在所述第二表面上沉积金属材料形成金属膜层，得到负极；最终得到一体化电池主体；Depositing a metal material on the second surface to form a metal film layer to obtain a negative electrode; finally obtaining an integrated battery body;
在惰性气体或无水环境下，然后将所述一体化电池主体装入电池壳体中，加入电解液后封装，得到一体化二次电池。 The integrated battery body is then placed in a battery case in an inert gas or waterless environment, and the electrolyte is added and packaged to obtain an integrated secondary battery.
本发明实施方式中，所述沉积的方式包括气相沉积、冷喷涂和热喷涂的中一种或多种，所述气相沉积包括物理气相沉积和化学气相沉积中的至少一种。进一步可选地的采用物理气相沉积技术，可以选自蒸发、溅射、电弧离子镀等，进一步可选的采用溅射技术。In an embodiment of the invention, the manner of depositing includes one or more of vapor deposition, cold spray, and thermal spray, and the vapor deposition includes at least one of physical vapor deposition and chemical vapor deposition. Further optionally, a physical vapor deposition technique may be employed, which may be selected from the group consisting of evaporation, sputtering, arc ion plating, etc., and further optionally using a sputtering technique.
本发明实施方式中，在所述第二表面上沉积金属材料形成金属箔的过程中，部分金属材料沉积在自所述第二表面向所述多孔隔膜内部延伸的孔洞中形成所述混合层，剩余金属材料沉积在所述第二表面上形成所述负极。In the embodiment of the present invention, in the process of depositing a metal material on the second surface to form a metal foil, a part of the metal material is deposited in a hole extending from the second surface toward the inside of the porous diaphragm to form the mixed layer. A remaining metal material is deposited on the second surface to form the negative electrode.
本发明实施方式中，所述涂覆的方式包括刮涂、旋涂、喷涂、滚涂和挤压涂布中的一种或多种。In an embodiment of the invention, the coating comprises one or more of knife coating, spin coating, spray coating, roll coating, and extrusion coating.
更具体地，本发明实施例还提供了一种上述二次电池的制备方法，包括以下步骤：More specifically, the embodiment of the present invention further provides a method for preparing the above secondary battery, comprising the following steps:
(1)隔膜制备：将多孔聚合物薄膜或多孔有机薄膜裁切成所需尺寸，然后清洗干净备用；(1) Diaphragm preparation: cutting a porous polymer film or a porous organic film into a desired size, and then cleaning it for use;
(2)电池正极活性材料制备：称取一定比例的正极活性材料、导电剂、粘结剂，加入适量溶剂进行机械研磨制成浆料，然后均匀涂覆于隔膜的一侧表面，然后进行干燥处理；所述溶剂可以选用N-甲基吡咯烷酮；(2) Preparation of positive electrode active material of battery: Weigh a certain proportion of positive active material, conductive agent and binder, add appropriate solvent to mechanically grind to make slurry, then uniformly apply to one side surface of the separator, and then dry it. Processing; the solvent may be selected from N-methylpyrrolidone;
(3)电池正极集流体制备：采用气相沉积技术进行正极集流体制备，具体是将一侧表面涂有正极材料的隔膜置于气相沉积腔室中，采用气相沉积技术将正极集流体源材料沉积到正极活性材料表面形成一定厚度的正极集流体膜层，所述正极集流体膜层的厚度为0.1μm-300μm，所述正极集流体源材料是导电材料，可以选自铝、铜、铁、锡、锌、镍、锰、钛、铅等的一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料；在正极集流体薄膜沉积过程中，采用特定治具遮蔽隔膜没有涂覆正极材料的另一侧表面及隔膜四周侧面，保证隔膜的该侧表面及隔膜四周侧面无薄膜沉积；正极集流体制备结束后，将表面涂覆有正极活性材料且正极活性材料表面沉积有正极集流体薄膜的隔膜从气相沉积腔室中取出备用；(3) Preparation of positive electrode current collector of battery: The preparation of positive electrode current collector is carried out by vapor deposition technique. Specifically, a separator coated with a positive electrode material on one side is placed in a vapor deposition chamber, and the positive current collector source material is deposited by vapor deposition technique. Forming a positive thickness current collector film layer having a thickness of 0.1 μm-300 μm to the surface of the positive electrode active material, the positive current collector material material being a conductive material, which may be selected from aluminum, copper, iron, One of tin, zinc, nickel, manganese, titanium, lead, or the like, or an alloy containing at least one of the above metal elements, or a composite material containing at least one of the above metal elements; in the deposition process of the positive electrode current collector film, specific The masking diaphragm is not coated with the other side surface of the cathode material and the side surface of the diaphragm, so that the side surface of the diaphragm and the side surface of the diaphragm are free of film deposition; after the preparation of the cathode current collector, the surface is coated with the positive electrode active material and the positive electrode. a separator having a positive current collector film deposited on the surface of the active material is taken out from the vapor deposition chamber for use;
(4)电池负极制备：采用气相沉积技术进行负极制备，具体将表面涂覆有正极活性材料且正极活性材料表面沉积有正极集流体薄膜的隔膜置于气相沉积 腔室中，将隔膜另一侧空白表面暴露于腔室中，并采用气相沉积技术将负极源材料沉积在隔膜的另一侧空白表面，形成一定厚度的薄膜，得到负极金属膜层，所述负极金属膜层的厚度为0.1μm-300μm，所述负极源材料是导体材料，可以选自铝、铜、铁、锡、锌、镍、锰、钛、铅等的一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料；在负极薄膜沉积过程中，采用特定治具遮蔽隔膜已经沉积正极集流体的那一面及四周侧面，保证已经沉积了正极集流体薄膜的表面及四周侧面无薄膜沉积；(4) Preparation of battery negative electrode: The negative electrode is prepared by vapor deposition technique, and the separator coated with the positive electrode active material on the surface and the positive electrode current collector film deposited on the surface of the positive electrode active material is placed in the vapor deposition layer. In the chamber, the blank surface of the other side of the diaphragm is exposed to the chamber, and the anode source material is deposited on the other blank surface of the separator by a vapor deposition technique to form a film of a certain thickness to obtain a negative metal film layer. The negative electrode metal film layer has a thickness of 0.1 μm to 300 μm, and the negative electrode source material is a conductor material, and may be selected from one of aluminum, copper, iron, tin, zinc, nickel, manganese, titanium, lead, or the like, or at least one An alloy of the above metal elements, or a composite material containing at least one of the above metal elements; in the deposition process of the negative electrode film, the side of the positive electrode current collector and the side surfaces of the positive electrode current collector are shielded by a specific fixture to ensure that the positive electrode set has been deposited. No film deposition on the surface and surrounding sides of the fluid film;
(5)电解液制备：量取一定体积的有机溶剂和添加剂，并混合均匀，然后称量一定质量的电解质，并加入到有机溶剂和添加剂的混合溶液中，充分搅拌均匀后备用；(5) Preparation of electrolyte: Measure a certain volume of organic solvent and additives, and mix well, then weigh a certain amount of electrolyte, and add it to the mixed solution of organic solvent and additive, stir well and reserve;
(6)电池组装：在惰性气体或无水环境下，将上述制备好的一体化结构装入电池壳体，然后加入适量电解液使隔膜完全浸润，然后封装完成电池组装。(6) Battery assembly: The above-prepared integrated structure is placed in a battery case under an inert gas or a waterless environment, and then an appropriate amount of electrolyte is added to completely infiltrate the separator, and then the package is completed.
需要说明的是尽管上述步骤(1)-(6)是以特定顺序描述了本发明二次电池制备方法的操作，但是，并非必须按照该特定顺序来执行这些操作。步骤(1)-(5)的操作可以同时或者任意先后执行。It is to be noted that although the above steps (1) to (6) describe the operation of the secondary battery preparation method of the present invention in a specific order, it is not necessary to perform these operations in this specific order. The operations of steps (1)-(5) can be performed simultaneously or in any order.
本发明实施例上述制备方法中应用到的原材料如前述实施例中所描述，此处不再赘述。The raw materials applied in the above preparation method of the present invention are as described in the foregoing embodiments, and are not described herein again.
本发明实施例第二方面提供的一体化二次电池的制备方法，简单易操作，可大大简化电池的制备工艺。The preparation method of the integrated secondary battery provided by the second aspect of the embodiment of the invention is simple and easy to operate, and the preparation process of the battery can be greatly simplified.
下面列举具体的实施例进一步说明上述二次电池的制备方法。The preparation method of the above secondary battery will be further described below by way of specific examples.
实施例1Example 1
采用金属铝作为负极活性材料和负极集流体，采用天然石墨作为正极活性材料，采用金属铝作为正极集流体，采用玻璃纤维纸作为隔膜，采用刮涂技术在玻璃纤维隔膜表面涂覆正极活性材料，并采用磁控溅射技术在正极活性材料表面和玻璃纤维隔膜的另一侧表面分别沉积正极集流体薄膜和负极薄膜，制备出具有一体化结构设计的铝-石墨双离子电池。Metal aluminum is used as the negative electrode active material and the negative electrode current collector, natural graphite is used as the positive electrode active material, metal aluminum is used as the positive electrode current collector, and glass fiber paper is used as the separator, and the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique. The positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side of the glass fiber separator by magnetron sputtering technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
一体化铝-石墨双离子电池的制备步骤如下： The preparation steps of the integrated aluminum-graphite dual ion battery are as follows:
(1)隔膜制备：将玻璃纤维纸裁切成70mm×140mm的矩形片，表面清洁干净后放入真空干燥箱中，在80℃条件下干燥24小时；(1) Preparation of the membrane: the glass fiber paper is cut into rectangular pieces of 70 mm×140 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
(2)电池正极材料制备：称取0.8g天然石墨、0.1g导电碳黑、0.1g聚偏氟乙烯，将三种材料混合均匀，然后加入2ml N-甲基吡咯烷酮充分研磨获得均匀浆料；然后将浆料均匀刮涂于玻璃纤维隔膜的一侧表面，然后放入真空干燥箱，在80℃条件下干燥12小时备用；(2) Preparation of battery positive electrode material: Weigh 0.8g natural graphite, 0.1g conductive carbon black, 0.1g polyvinylidene fluoride, mix the three materials uniformly, and then fully grind 2ml N-methylpyrrolidone to obtain a uniform slurry; Then, the slurry is uniformly sprayed on one side surface of the glass fiber membrane, and then placed in a vacuum drying oven and dried at 80 ° C for 12 hours for use;
(3)电池正极集流体制备：采用V-Tech MF610/610型多功能离子镀膜***进行电池正极集流体的制备，选用的溅射靶材为金属铝，尺寸为300mm×100mm×10mm，纯度为99.5％。将一侧表面涂有正极活性材料的玻璃纤维纸放入镀膜***的腔室内，将涂有正极活性材料的一面与金属铝靶相对，设定靶材与玻璃纤维纸的距离为65mm。为了最大限度降低沉积腔室内的水和氧的含量，在沉积开始前将腔室的真空度抽到2×10-3Pa或更高。然后通入氩气使工作气压为0.8Pa，并施加-800V的直流偏压，以产生辉光放电对玻璃纤维隔膜和正极活性材料进行等离子体清洗，以进一步去除其中的水和氧气。等离子体清洗结束以后，开启铝磁控靶进行铝薄膜沉积，设定靶功率为2.4kW，偏压为-30V，工作气压为0.5Pa，沉积时间设定为1小时，沉积得到的正极集流体薄膜厚度为25μm。在沉积过程中，玻璃纤维隔膜固定于不锈钢材质的特殊治具中，所述治具将玻璃纤维纸没有涂覆正极活性材料的另一侧表面及四周侧面遮蔽，并保证整个沉积过程中该表面及四周侧面没有薄膜沉积；(3) Preparation of battery positive current collector: The V-Tech MF610/610 multi-functional ion plating system was used to prepare the battery positive current collector. The selected sputtering target was metal aluminum, the size was 300mm×100mm×10mm, and the purity was 99.5%. A glass fiber paper coated with a positive electrode active material on one side was placed in a chamber of a coating system, and a side coated with a positive electrode active material was opposed to a metal aluminum target, and a distance between the target and the glass fiber paper was set to 65 mm. In order to minimize the water and oxygen content in the deposition chamber, the vacuum of the chamber is drawn to 2 × 10 -3 Pa or higher before the deposition starts. Then, argon gas was introduced to bring the working pressure to 0.8 Pa, and a DC bias of -800 V was applied to generate a glow discharge to plasma-clean the glass fiber separator and the positive electrode active material to further remove water and oxygen therein. After the plasma cleaning is completed, the aluminum magnetron target is opened for aluminum film deposition, and the target power is set to 2.4 kW, the bias voltage is -30 V, the working pressure is 0.5 Pa, the deposition time is set to 1 hour, and the obtained positive electrode current collector is deposited. The film thickness was 25 μm. During the deposition process, the glass fiber membrane is fixed in a special fixture made of stainless steel, which shields the other side surface and the peripheral side of the glass fiber paper which is not coated with the positive electrode active material, and ensures the surface during the entire deposition process. And no film deposition on the sides;
(4)电池负极制备：电池正极集流体薄膜沉积结束后，将一侧涂有正极集流体铝薄膜的玻璃纤维纸反转放置于治具中，使另一侧没有薄膜沉积的表面暴露于腔室中，并与金属铝靶相对放置，且设定靶材与玻璃纤维纸之间的距离为65mm。后续采用与制备正极集流体铝薄膜相同的制备工艺进行负极铝薄膜的沉积，沉积时间设定为1小时，沉积得到的负极铝薄膜厚度为25μm。最终制得一体化电池主体；(4) Preparation of battery negative electrode: After the deposition of the positive electrode current collector film of the battery is completed, the glass fiber paper coated with the positive electrode current collector aluminum film on one side is reversely placed in the jig, and the surface on the other side without film deposition is exposed to the cavity. The chamber was placed opposite to the metal aluminum target, and the distance between the target and the glass fiber paper was set to 65 mm. Subsequently, the deposition of the negative electrode aluminum film was carried out by the same preparation process as the preparation of the positive electrode current collector aluminum film, and the deposition time was set to 1 hour, and the thickness of the deposited negative electrode aluminum film was 25 μm. Finally, an integrated battery body is produced;
(5)电解液制备：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，配置成4M的电解液，然后加入质量分数为4％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后备用； (5) Preparation of electrolyte: Weigh 3g of lithium hexafluorophosphate into 5ml of ethyl methyl carbonate, stir until lithium hexafluorophosphate is completely dissolved, configure it into 4M electrolyte, then add 4% by mass of vinylene carbonate as additive, stir well Even after standby;
(6)电池组装：将上述制备好的一体化电池主体，即一侧表面涂覆正极活性材料且两侧沉积铝薄膜的玻璃纤维纸裁切成直径为16mm的圆片，然后在氩气气氛保护的手套箱中，将圆片放入扣式电池壳中，滴入适量电解液然后封装完成电池组装。(6) Battery assembly: The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then in an argon atmosphere. In the protected glove box, put the wafer into the button battery case, drop the appropriate amount of electrolyte and then complete the battery assembly.
采用武汉市蓝电电子股份有限公司的LAND测试***对制备的二次电池进行电化学性能测试，测试结果如图2、图3和图4所示。由图2(a)和2(b)可见，本发明实施例所制备的铝-石墨二次电池在高达120C的倍率条件下，放电比容量依然高达116.6mAh/g，是在1C倍率下放电比容量(120.6mAh/g)的96.7％。图2(c)进一步证实了本发明实施例所制备的铝-石墨二次电池的超高倍率性能和优异的库伦效率。另外，本发明实施例所制备的铝-石墨二次电池在超高倍率条件下还具有优异的循环性能，如图2(d)所示，在60C的超高倍率下，二次电池的循环次数超过1500圈，而且在前200圈，电池放电比容量几乎保持122mAh/g无衰减，具有接近100％的容量保持率；200圈之后虽然容量出现一定的衰减，500圈之后比容量趋于稳定，并依然保持高达72mAh/g的放电比容量。特别的，本发明实施例甚至在高达120C的倍率条件下，依然具有高的循环性能，如图3所示，在120C的超高倍率下，电池的循环次数依然可以达到200圈，且具有高达102mAh/g的可逆放电比容量。The electrochemical performance of the prepared secondary battery was tested by the LAND test system of Wuhan Landian Electronics Co., Ltd. The test results are shown in Fig. 2, Fig. 3 and Fig. 4. 2(a) and 2(b), the aluminum-graphite secondary battery prepared in the embodiment of the present invention has a discharge specific capacity of up to 116.6 mAh/g at a rate of up to 120 C, which is discharged at a rate of 1 C. 96.7% of specific capacity (120.6 mAh/g). Fig. 2(c) further demonstrates the ultrahigh rate performance and excellent coulombic efficiency of the aluminum-graphite secondary battery prepared by the embodiment of the present invention. In addition, the aluminum-graphite secondary battery prepared by the embodiment of the invention has excellent cycle performance under ultra high rate conditions, as shown in FIG. 2(d), the cycle of the secondary battery at an ultrahigh magnification of 60C. The number of times exceeds 1500 laps, and in the first 200 laps, the battery discharge capacity is almost 122 mAh/g without attenuation, and has a capacity retention rate close to 100%. After 200 laps, although the capacity has a certain attenuation, the specific capacity tends to be stable after 500 laps. And still maintain a discharge specific capacity of up to 72mAh / g. In particular, the embodiment of the present invention still has high cycle performance even under the condition of a magnification of up to 120 C. As shown in FIG. 3, at an ultra-high magnification of 120 C, the number of cycles of the battery can still reach 200 laps, and has a high Reversible discharge specific capacity of 102 mAh / g.
本发明实施例所制备的铝-石墨二次电池之所以呈现超高的倍率性能，主要是因为本发明二次电池的独特结构设计和制备方法，如图4所示，本发明实施例将正极集流体直接沉积在正极石墨活性材料表面，如图4(b)所示，集流体与活性材料之间具有良好的界面接触，使得电池的接触电阻降低。另外，如图4(a)所示，由于负极铝薄膜直接沉积于具有多孔结构的玻璃纤维纸表面，使得负极铝薄膜也具有3D多孔结构，这种3D多孔结构可以为电子和离子的扩散提供有效的路径，可有效提高电池的倍率性能。The reason why the aluminum-graphite secondary battery prepared by the embodiment of the present invention exhibits ultra-high rate performance is mainly because of the unique structural design and preparation method of the secondary battery of the present invention, as shown in FIG. 4, the positive electrode of the embodiment of the present invention The current collector is directly deposited on the surface of the positive electrode graphite active material. As shown in FIG. 4(b), the interface between the current collector and the active material has good interface contact, so that the contact resistance of the battery is lowered. In addition, as shown in FIG. 4(a), since the negative aluminum film is directly deposited on the surface of the glass fiber paper having a porous structure, the negative aluminum film also has a 3D porous structure, and the 3D porous structure can provide diffusion of electrons and ions. An effective path can effectively improve the rate performance of the battery.
为了进一步解释本发明实施例所制备二次电池的超高倍率性能，对所制备一体化铝-石墨二次电池的电化学阻抗谱进行测试，为了便于比较，同时测试了本团队前期所报道以铝箔为负极，以天然石墨为正极，并采用玻璃纤维纸为隔膜的常规铝-石墨双离子电池的电化学阻抗谱。为了保证可比性，常规铝-石墨双 离子电池所采用的隔膜以及电解液包括封装条件均与本发明实施例所制备的一体化铝-石墨二次电池严格保持一致。在2C条件下两种电池循环100圈之后进行电化学阻抗谱测试，测试结果如图5所示，根据等效电路拟合计算可得，本发明实施例所制备的一体化铝-石墨二次电池的接触电阻Rs和电荷转移电阻Rct分别为8.55Ω和20.7Ω，远低于常规铝-石墨双离子电池的接触电阻(Rs＝10.3Ω)和电荷转移电阻(Rct＝128.1Ω)。In order to further explain the ultra-high rate performance of the secondary battery prepared by the embodiment of the present invention, the electrochemical impedance spectroscopy of the prepared integrated aluminum-graphite secondary battery was tested, and for the sake of comparison, the previous report of the team was also tested. The aluminum foil is a negative electrode, the natural graphite is used as a positive electrode, and the electrochemical impedance spectrum of a conventional aluminum-graphite dual ion battery using glass fiber paper as a separator is used. In order to ensure comparability, the separators and electrolytes used in conventional aluminum-graphite dual ion batteries, including the packaging conditions, are strictly consistent with the integrated aluminum-graphite secondary batteries prepared in the examples of the present invention. The electrochemical impedance spectroscopy test was performed after the two batteries were cycled for 100 cycles under the condition of 2C. The test results are shown in Fig. 5. According to the equivalent circuit fitting calculation, the integrated aluminum-graphite prepared by the embodiment of the present invention is twice. The contact resistance R s and the charge transfer resistance R ct of the battery are 8.55 Ω and 20.7 Ω, respectively, which are much lower than the contact resistance (R s = 10.3 Ω) and charge transfer resistance (R ct = 128.1 Ω) of a conventional aluminum-graphite dual ion battery. ).
同时，估算了本发明实施例所制备的电池能量密度和功率密度如表1所示，并与其它常用储能器件如锂离子电池、铅酸电池、镍氢电池以及超级电容器进行了比较，如图6所示。由图6可见，本发明实施例所制备的铝-石墨二次电池的能量密度和功率密度远高于常规锂离子电池，铅酸电池和镍氢电池，具有与超级电容器相当的超高功率密度。At the same time, it is estimated that the energy density and power density of the battery prepared by the embodiment of the present invention are as shown in Table 1, and compared with other commonly used energy storage devices such as lithium ion batteries, lead acid batteries, nickel hydrogen batteries and super capacitors, such as Figure 6 shows. It can be seen from FIG. 6 that the energy density and power density of the aluminum-graphite secondary battery prepared by the embodiment of the present invention are much higher than that of the conventional lithium ion battery, the lead acid battery and the nickel hydrogen battery, and have an ultra high power density comparable to that of the super capacitor. .
表1.本发明实施例1所制备铝-石墨二次电池在不同倍率下的能量密度和功率密度(Ec和Pc分别为基于正极活性物质质量计算的正极活性物质能量密度和功率密度，Ecell和Pcell分别为所组装铝-石墨二次电池的能量密度和功率密度，t为放电时间)Table 1. Preparation Example 1 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
Figure PCTCN2017078205-appb-000001
Figure PCTCN2017078205-appb-000001
实施例2 Example 2
采用金属铝作为负极活性材料和负极集流体，采用天然石墨作为正极活性材料，采用金属铝作为正极集流体，采用玻璃纤维纸作为隔膜，采用刮涂技术在玻璃纤维隔膜表面涂覆正极活性材料，并采用热蒸发镀膜技术在正极活性材料表面和玻璃纤维隔膜的另一侧表面分别沉积正极集流体薄膜和负极薄膜，制备出具有一体化结构设计的铝-石墨双离子电池。Metal aluminum is used as the negative electrode active material and the negative electrode current collector, natural graphite is used as the positive electrode active material, metal aluminum is used as the positive electrode current collector, and glass fiber paper is used as the separator, and the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique. The positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side of the glass fiber separator by thermal evaporation coating technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
所述一体化铝-石墨双离子电池的制备步骤如下：The preparation steps of the integrated aluminum-graphite dual ion battery are as follows:
(1)隔膜制备：将玻璃纤维纸裁切成50mm×100mm的矩形片，表面清洁干净后放入真空干燥箱中，在80℃条件下干燥24小时；(1) Preparation of the separator: the glass fiber paper is cut into rectangular pieces of 50 mm×100 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
(2)电池正极材料制备：称取0.4g天然石墨、0.05g导电碳黑、0.05g聚偏氟乙烯，将三种材料混合均匀，然后加入1ml N-甲基吡咯烷酮充分研磨获得均匀浆料；然后将浆料均匀刮涂于玻璃纤维隔膜的一侧表面，然后放入真空干燥箱，在80℃条件下干燥12小时备用；(2) Preparation of battery positive electrode material: Weigh 0.4g natural graphite, 0.05g conductive carbon black, 0.05g polyvinylidene fluoride, mix the three materials uniformly, and then fully grind 1ml N-methylpyrrolidone to obtain a uniform slurry; Then, the slurry is uniformly sprayed on one side surface of the glass fiber membrane, and then placed in a vacuum drying oven and dried at 80 ° C for 12 hours for use;
(3)电池正极集流体与电池负极制备：采用真空蒸镀***进行电池正极集流体的制备，选用纯度为99.9％的铝丝作为蒸发源材料，采用钨丝进行加热使铝丝气化。将一侧表面涂有正极活性材料的玻璃纤维纸垂直悬挂与镀膜***的腔室内，设定蒸发源与玻璃纤维纸的距离为200mm。为了最大限度降低沉积腔室内的水和氧的含量，在沉积开始前将腔室的真空度抽到2×10-3Pa或更高。打开钨丝加热电源，使铝丝气化蒸发并在玻璃纤维纸的两个表面均匀沉积铝薄膜，沉积时间设定为1小时，沉积得到的正极集流体薄膜和负极铝薄膜的厚度均为20μm。在沉积过程中，玻璃纤维隔膜固定于不锈钢材质的特殊治具中，所述治具将玻璃纤维纸的四周侧面遮蔽，并保证隔膜两侧表面暴露于镀膜腔室中。最终制得一体化电池主体；(3) Preparation of battery positive current collector and battery negative electrode: The vacuum positive electrode current collector was prepared by vacuum evaporation system. The aluminum wire with purity of 99.9% was selected as the evaporation source material, and the aluminum wire was gasified by heating with tungsten wire. A glass fiber paper coated with a positive electrode active material on one side was vertically suspended and chambered in the coating system, and the distance between the evaporation source and the glass fiber paper was set to 200 mm. In order to minimize the water and oxygen content in the deposition chamber, the vacuum of the chamber is drawn to 2 × 10 -3 Pa or higher before the deposition starts. The tungsten wire heating power source is turned on, the aluminum wire is vaporized and evaporated, and the aluminum film is uniformly deposited on both surfaces of the glass fiber paper, and the deposition time is set to 1 hour, and the thickness of the deposited positive electrode current collector film and the negative electrode aluminum film is 20 μm. . During the deposition process, the fiberglass membrane is fixed in a special fixture made of stainless steel, which shields the sides of the fiberglass paper and ensures that both sides of the membrane are exposed to the coating chamber. Finally, an integrated battery body is produced;
(4)电解液制备：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，配置成4M的电解液，然后加入质量分数为4％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后备用；(4) Preparation of electrolyte: Weigh 3g of lithium hexafluorophosphate into 5ml of ethyl methyl carbonate, stir until lithium hexafluorophosphate is completely dissolved, configure it into 4M electrolyte, then add 4% by mass of vinylene carbonate as additive, stir well Even after standby;
(5)电池组装：将上述制备好的一体化电池主体，即一侧表面涂覆正极活性材料且两侧沉积铝薄膜的玻璃纤维纸裁切成直径为16mm的圆片，然后在氩气 气氛保护的手套箱中，将圆片放入扣式电池壳中，滴入适量电解液然后封装完成电池组装。(5) Battery assembly: The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then argon gas. In the atmosphere-protected glove box, the wafer is placed in a button-type battery case, an appropriate amount of electrolyte is dropped, and the battery assembly is completed.
采用武汉市蓝电电子股份有限公司的LAND测试***对制备的二次电池进行电化学性能测试，测试结果如表2所示。由表2可见，采用蒸发镀膜工艺进行正极集流体和负极制备所获得的铝-石墨二次电池具有与具体实施例1相近的超高倍率性能。The prepared secondary battery was tested for electrochemical performance using the LAND test system of Wuhan Landian Electronics Co., Ltd. The test results are shown in Table 2. As can be seen from Table 2, the aluminum-graphite secondary battery obtained by performing the positive electrode current collector and the negative electrode preparation by the evaporation coating process has an ultrahigh rate performance similar to that of the specific embodiment 1.
表2.本发明实施例2所制备铝-石墨二次电池在不同倍率下的能量密度和功率密度(Ec和Pc分别为基于正极活性物质质量计算的正极活性物质能量密度和功率密度，Ecell和Pcell分别为所组装铝-石墨二次电池的能量密度和功率密度，t为放电时间)Table 2. Preparation Example 2 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
Figure PCTCN2017078205-appb-000002
Figure PCTCN2017078205-appb-000002
实施例3Example 3
采用金属铝作为负极活性材料和负极集流体，采用天然石墨作为正极活性材料，采用金属铝作为正极集流体，采用玻璃纤维纸作为隔膜，采用刮涂技术在玻璃纤维隔膜表面涂覆正极活性材料，并采用电弧离子镀技术在正极活性材料表面和玻璃纤维隔膜的另一侧表面分别沉积正极集流体薄膜和负极薄膜，制备出具有一体化结构设计的铝-石墨双离子电池。 Metal aluminum is used as the negative electrode active material and the negative electrode current collector, natural graphite is used as the positive electrode active material, metal aluminum is used as the positive electrode current collector, and glass fiber paper is used as the separator, and the positive electrode active material is coated on the surface of the glass fiber separator by the doctor blade technique. The positive electrode current collector film and the negative electrode film were deposited on the surface of the positive electrode active material and the other side surface of the glass fiber separator by arc ion plating technology to prepare an aluminum-graphite dual ion battery with integrated structure design.
所述一体化铝-石墨双离子电池的制备步骤如下：The preparation steps of the integrated aluminum-graphite dual ion battery are as follows:
(1)隔膜制备：将玻璃纤维纸裁切成60mm×120mm的矩形片，表面清洁干净后放入真空干燥箱中，在80℃条件下干燥24小时；(1) Preparation of the separator: the glass fiber paper is cut into rectangular pieces of 60 mm×120 mm, the surface is cleaned, placed in a vacuum drying oven, and dried at 80 ° C for 24 hours;
(2)电池正极材料制备：称取0.8g天然石墨、0.1g导电碳黑、0.1g聚偏氟乙烯，将三种材料混合均匀，然后加入2ml N-甲基吡咯烷酮充分研磨获得均匀浆料；然后将浆料均匀刮涂于玻璃纤维隔膜的一侧表面，然后放入真空干燥箱，在80℃条件下干燥12小时备用；(2) Preparation of battery positive electrode material: Weigh 0.8g natural graphite, 0.1g conductive carbon black, 0.1g polyvinylidene fluoride, mix the three materials uniformly, and then fully grind 2ml N-methylpyrrolidone to obtain a uniform slurry; Then, the slurry is uniformly sprayed on one side surface of the glass fiber membrane, and then placed in a vacuum drying oven and dried at 80 ° C for 12 hours for use;
(3)电池正极集流体与电池负极制备：采用电弧离子镀***进行电池正极集流体的制备，选用纯度为99.5％的铝作为电弧靶材，靶材直径为150mm，厚度为20mm。将一侧表面涂有正极活性材料的玻璃纤维纸垂直悬挂于镀膜转架上，设定铝电弧靶与玻璃纤维纸的距离为120mm。为了最大限度降低沉积腔室内的水和氧的含量，在沉积开始前将腔室的真空度抽到2×10-3Pa或更高。然后通入氩气使工作气压为1.0Pa，并施加-900V的直流偏压，以产生辉光放电对玻璃纤维隔膜和正极活性材料进行等离子体清洗，以进一步去除其中的水和氧气。等离子体清洗结束以后，开启铝电弧靶在玻璃纤维纸的两个表面同时进行铝薄膜沉积，为了保证薄膜沉积的均匀性，薄膜在沉积过程中玻璃纤维纸随转架进行公自转。设定靶电流为60A，靶电压为20V，偏压为-10V，工作气压为0.8Pa，沉积时间设定为3小时，沉积得到的正极集流体薄膜厚度为50μm。在沉积过程中，玻璃纤维隔膜固定于不锈钢材质的特殊治具中，所述治具将玻璃纤维纸的四周侧面遮蔽，并保证隔膜两侧表面暴露于镀膜腔室中。最终制得一体化电池主体；(3) Preparation of battery positive current collector and battery negative electrode: The electrode positive current collector was prepared by arc ion plating system, and aluminum with purity of 99.5% was selected as the arc target. The target diameter was 150 mm and the thickness was 20 mm. A glass fiber paper coated with a positive electrode active material on one side was vertically suspended on the coating turret, and the distance between the aluminum arc target and the glass fiber paper was set to be 120 mm. In order to minimize the water and oxygen content in the deposition chamber, the vacuum of the chamber is drawn to 2 × 10 -3 Pa or higher before the deposition starts. Then, argon gas was introduced to bring the working pressure to 1.0 Pa, and a DC bias of -900 V was applied to generate a glow discharge to plasma-clean the glass fiber separator and the positive electrode active material to further remove water and oxygen therein. After the plasma cleaning is finished, the aluminum arc target is opened to simultaneously deposit aluminum film on both surfaces of the glass fiber paper. In order to ensure the uniformity of film deposition, the glass fiber paper is rotated with the rotating body during the deposition process. The target current was set to 60 A, the target voltage was 20 V, the bias voltage was -10 V, the working gas pressure was 0.8 Pa, the deposition time was set to 3 hours, and the deposited positive electrode current collector film was 50 μm thick. During the deposition process, the fiberglass membrane is fixed in a special fixture made of stainless steel, which shields the sides of the fiberglass paper and ensures that both sides of the membrane are exposed to the coating chamber. Finally, an integrated battery body is produced;
(4)电解液制备：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，配置成4M的电解液，然后加入质量分数为4％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后备用；(4) Preparation of electrolyte: Weigh 3g of lithium hexafluorophosphate into 5ml of ethyl methyl carbonate, stir until lithium hexafluorophosphate is completely dissolved, configure it into 4M electrolyte, then add 4% by mass of vinylene carbonate as additive, stir well Even after standby;
(5)电池组装：将上述制备好的一体化电池主体，即一侧表面涂覆正极活性材料且两侧沉积铝薄膜的玻璃纤维纸裁切成直径为16mm的圆片，然后在氩气气氛保护的手套箱中，将圆片放入扣式电池壳中，滴入适量电解液然后封装完成电池组装。 (5) Battery assembly: The integrated battery body prepared above, that is, a glass fiber paper coated with a positive electrode active material on one side and an aluminum film deposited on both sides is cut into a disk having a diameter of 16 mm, and then in an argon atmosphere. In the protected glove box, put the wafer into the button battery case, drop the appropriate amount of electrolyte and then complete the battery assembly.
采用武汉市蓝电电子股份有限公司的LAND测试***对制备的二次电池进行电化学性能测试，测试结果如表3所示。由表3可见，采用电弧离子镀技术进行正极集流体和负极制备所获得的铝-石墨二次电池具有与具体实施例1和具体实施例3相比，能量密度和功率密度有所降低，主要原因是电弧离子镀技术离子能量高，使得负极铝薄膜结构更加致密，导致其孔隙率降低，不过依然具有超高倍率性能。The prepared secondary battery was tested for electrochemical performance using the LAND test system of Wuhan Landian Electronics Co., Ltd. The test results are shown in Table 3. It can be seen from Table 3 that the aluminum-graphite secondary battery obtained by the positive electrode current collector and the negative electrode preparation by the arc ion plating technique has a lower energy density and power density than that of the specific embodiment 1 and the specific embodiment 3. The reason is that the ion energy of the arc ion plating technology is high, which makes the structure of the negative aluminum film more dense, resulting in a decrease in porosity, but still has ultra high rate performance.
表3.本发明实施例3所制备铝-石墨二次电池在不同倍率下的能量密度和功率密度(Ec和Pc分别为基于正极活性物质质量计算的正极活性物质能量密度和功率密度，Ecell和Pcell分别为所组装铝-石墨二次电池的能量密度和功率密度，t为放电时间)Table 3. Preparation Example 3 of the present invention embodiments an aluminum - graphite secondary battery under different rates of energy density and power density (E c and P c are respectively a positive electrode active material energy density and power density is calculated based on the quality of the positive electrode active material, E cell and P cell are the energy density and power density of the assembled aluminum-graphite secondary battery, respectively, t is the discharge time)
Figure PCTCN2017078205-appb-000003
Figure PCTCN2017078205-appb-000003
实施例4-13Example 4-13
实施例4-13与实施例1的二次电池制备过程中除了制备电池负极和正极集流体使用的溅射靶材不同外，其他所有步骤及使用的材料都相同，同时对实施例4-13的二次电池进行电池的电化学性能测试，并与本发明实施例1的性能进行比较，实施例4-13所使用的负极材料及其电化学性能具体参见表4。The preparation of the secondary battery of Examples 4-13 and Example 1 was the same except that the sputtering target used for preparing the battery negative electrode and the positive electrode current collector was the same, and all the other steps and materials used were the same, and Examples 4-13 were The secondary battery was tested for electrochemical performance of the battery and compared with the performance of Example 1 of the present invention. The negative electrode materials used in Examples 4-13 and their electrochemical properties are detailed in Table 4.
表4.本发明实施例4-13的二次电池的电化学性能数据表 Table 4. Electrochemical performance data sheets of secondary batteries of Examples 4-13 of the present invention
Figure PCTCN2017078205-appb-000004
Figure PCTCN2017078205-appb-000004
从表4可以看出，本发明实施例中，负极集流体为铝薄膜，其能量密度和功率密度高，循环性能好。As can be seen from Table 4, in the embodiment of the present invention, the anode current collector is an aluminum film, which has high energy density and power density, and good cycle performance.
实施例14-36Example 14-36
实施例14-36与实施例1的二次电池制备过程中除了制备电池正极活性材料不同之外，其他所有步骤和使用的材料都相同，同时对实施例14-36的二次电池 的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例14-36所使用的正极活性材料及其电化学性能具体参见表5。All of the steps and materials used in the preparation of the secondary batteries of Examples 14-36 and Example 1 were the same except that the battery positive active material was prepared, and the secondary batteries of Examples 14-36 were simultaneously used. The electrochemical performance was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 14-36 and their electrochemical properties are detailed in Table 5.
表5.本发明实施例14-36的二次电池的电化学性能数据表Table 5. Electrochemical performance data sheets of secondary batteries of Examples 14 to 36 of the present invention
Figure PCTCN2017078205-appb-000005
Figure PCTCN2017078205-appb-000005
Figure PCTCN2017078205-appb-000006
Figure PCTCN2017078205-appb-000006
从表5可以看出，本发明实施例中，正极活性材料为天然石墨，其能量密度和功率密度高。As can be seen from Table 5, in the embodiment of the present invention, the positive electrode active material is natural graphite, and its energy density and power density are high.
实施例37-43Examples 37-43
实施例37-43与实施例1的二次电池制备过程中除了制备电解液使用的电解质不同之外，其他所有步骤和使用的材料都相同，同时对实施例37-43的二次电 池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例37-43所使用的正极活性材料及其电化学性能具体参见表6。The preparation of the secondary batteries of Examples 37-43 and Example 1 was the same except that the electrolyte used to prepare the electrolyte was the same, and all the other steps and materials used were the same, while the secondary electricity of Examples 37-43 was The electrochemical performance of the cell was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 37-43 and their electrochemical properties are detailed in Table 6.
表6.本发明实施例37-43的二次电池的电化学性能数据表Table 6. Electrochemical performance data sheets of secondary batteries of Examples 37 to 43 of the present invention
Figure PCTCN2017078205-appb-000007
Figure PCTCN2017078205-appb-000007
从表6可以看出，本发明实施例中，电解质为六氟磷酸锂，其能量密度和功率密度高，循环性能好。As can be seen from Table 6, in the embodiment of the present invention, the electrolyte is lithium hexafluorophosphate, which has high energy density and power density, and good cycle performance.
实施例44-48Example 44-48
实施例44-48与实施例1的二次电池制备过程中除了制备电解液使用的电解质浓度不同之外，其他所有步骤和使用的材料都相同，同时对实施例44-48的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例44-48所使用的正极活性材料及其电化学性能具体参见表7。All of the steps and materials used in the preparation of the secondary batteries of Examples 44-48 and Example 1 except for the electrolyte concentration used to prepare the electrolyte were the same, while the secondary batteries of Examples 44-48 were The electrochemical performance was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 44-48 and their electrochemical properties are detailed in Table 7.
表7.本发明实施例44-48的二次电池的电化学性能数据表 Table 7. Electrochemical performance data sheets of secondary batteries of Examples 44 to 48 of the present invention
Figure PCTCN2017078205-appb-000008
Figure PCTCN2017078205-appb-000008
从表7可以看出，本发明实施例中，电解质浓度为4M，其能量密度和功率密度高，循环性能好。As can be seen from Table 7, in the embodiment of the present invention, the electrolyte concentration is 4M, the energy density and power density are high, and the cycle performance is good.
实施例49-58Example 49-58
实施例49-58与实施例1的二次电池制备过程中除了制备电解液使用的溶剂材料不同之外，其他所有步骤和使用的材料都相同，同时对实施例49-58的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例49-58所使用的正极活性材料及其电化学性能具体参见表8。All of the steps and materials used in the preparation of the secondary batteries of Examples 49 to 58 and Example 1 were the same except that the solvent materials used for the preparation of the electrolytic solution were different, while the secondary batteries of Examples 49 to 58 were used. The electrochemical performance was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 49-58 and their electrochemical properties are detailed in Table 8.
表8.本发明实施例49-58的二次电池的电化学性能数据表Table 8. Electrochemical performance data sheets of secondary batteries of Examples 49 to 58 of the present invention
Figure PCTCN2017078205-appb-000009
Figure PCTCN2017078205-appb-000009
Figure PCTCN2017078205-appb-000010
Figure PCTCN2017078205-appb-000010
从表8可以看出，本发明实施例中，溶剂为碳酸甲乙酯，其能量密度和功率密度高。As can be seen from Table 8, in the examples of the present invention, the solvent is ethyl methyl carbonate, which has high energy density and power density.
实施例59-66Examples 59-66
实施例59-66与实施例1的二次电池制备过程中除了制备电解液使用的添加剂种类不同之外，其他所有步骤和使用的材料都相同，同时对实施例59-66的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例59-66所使用的正极活性材料及其电化学性能具体参见表9。All of the steps and materials used in the preparation of the secondary batteries of Examples 59-66 and Example 1 except for the types of additives used to prepare the electrolyte were the same, while the secondary batteries of Examples 59-66 were The electrochemical performance was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 59-66 and their electrochemical properties are shown in Table 9.
表9.本发明实施例59-66的二次电池的电化学性能数据表Table 9. Electrochemical performance data sheets of secondary batteries of Examples 59-66 of the present invention
Figure PCTCN2017078205-appb-000011
Figure PCTCN2017078205-appb-000011
Figure PCTCN2017078205-appb-000012
Figure PCTCN2017078205-appb-000012
从表9可以看出，本发明实施例中，添加剂种类为碳酸亚乙烯酯，其循环性能好。As can be seen from Table 9, in the examples of the present invention, the type of the additive is vinylene carbonate, and the cycle performance is good.
实施例67-73Examples 67-73
实施例67-73与实施例1的二次电池制备过程中除了制备电解液使用的添加剂浓度不同之外，其他所有步骤和使用的材料都相同，同时对实施例67-73的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例67-73所使用的正极活性材料及其电化学性能具体参见表10。All of the steps and materials used in the preparation of the secondary batteries of Examples 67-73 and Example 1 except for the concentration of the additive used to prepare the electrolytic solution were the same, while the secondary batteries of Examples 67-73 were used. The electrochemical performance was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 67-73 and their electrochemical properties are shown in Table 10.
表10.本发明实施例67-73的二次电池的电化学性能数据表Table 10. Electrochemical performance data sheets of secondary batteries of Examples 67 to 73 of the present invention
Figure PCTCN2017078205-appb-000013
Figure PCTCN2017078205-appb-000013
Figure PCTCN2017078205-appb-000014
Figure PCTCN2017078205-appb-000014
从表10可以看出，本发明实施例中，添加剂质量含量为4％时，其循环稳定性好。As can be seen from Table 10, in the examples of the present invention, when the additive content is 4%, the cycle stability is good.
实施例74-77Example 74-77
实施例74-77与实施例1的二次电池制备过程中除了所使用的隔膜材料不同之外，其他所有步骤和使用的材料都相同，同时对实施例74-77的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例74-77所使用的正极活性材料及其电化学性能具体参见表11。All of the steps and materials used in the preparation of the secondary batteries of Examples 74-77 and Example 1 were the same except that the separator material used was the same, and the electrochemical treatment of the secondary batteries of Examples 74-77 was also carried out. The properties were tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 74-77 and their electrochemical properties are detailed in Table 11.
表11.本发明实施例74-77的二次电池的电化学性能数据表Table 11. Electrochemical performance data sheets of secondary batteries of Examples 74-77 of the present invention
Figure PCTCN2017078205-appb-000015
Figure PCTCN2017078205-appb-000015
Figure PCTCN2017078205-appb-000016
Figure PCTCN2017078205-appb-000016
从表11可以看出，本发明实施例中，隔膜为玻璃纤维纸，其能量密度和功率密度高，循环性能好。As can be seen from Table 11, in the embodiment of the present invention, the separator is glass fiber paper, which has high energy density and power density, and good cycle performance.
实施例78-84Examples 78-84
实施例78-84与实施例1的二次电池制备过程中除了所使用的导电剂、粘结剂种类和质量分数不同之外，其他所有步骤和使用的材料都相同，同时对实施例78-84的二次电池的电化学性能进行测试，并与本发明实施例1的性能进行比较，实施例78-84所使用的正极活性材料及其电化学性能具体参见表12。All of the steps and materials used in the preparation of the secondary batteries of Examples 78-84 and Example 1 were the same except that the conductive agent, the type of the binder and the mass fraction used were different, and the same was carried out for Example 78- The electrochemical performance of the secondary battery of 84 was tested and compared with the performance of Example 1 of the present invention. The positive electrode active materials used in Examples 78-84 and their electrochemical properties are shown in Table 12.
表12.本发明实施例78-84的二次电池的电化学性能数据表Table 12. Electrochemical performance data sheets of secondary batteries of Examples 78-84 of the present invention
Figure PCTCN2017078205-appb-000017
Figure PCTCN2017078205-appb-000017
Figure PCTCN2017078205-appb-000018
Figure PCTCN2017078205-appb-000018
从表12可以看出，本发明实施例中，隔膜为玻璃纤维纸，其能量密度和功率密度高，循环性能好。As can be seen from Table 12, in the embodiment of the present invention, the separator is a glass fiber paper, which has high energy density and power density, and good cycle performance.
本发明实施例涉及的二次电池形态不局限于扣式电池，也可根据核心成分设计成平板电池、圆柱电池等形态。本发明实施例的二次电池主要活性成分为可供钾盐阴离子脱出与嵌入的材料，且电池体系中无需负极活性材料，因而可显著降低电池自重和制备成本，提升电池能量密度，同时该电池具有优异的循环稳定性能，在二次电池领域具有广阔的应用前景。 The secondary battery according to the embodiment of the present invention is not limited to the button battery, and may be designed in the form of a flat battery or a cylindrical battery according to the core component. The main active component of the secondary battery of the embodiment of the invention is a material for the potassium salt anion to be extracted and embedded, and the negative electrode active material is not needed in the battery system, thereby significantly reducing the battery weight and the preparation cost, and improving the energy density of the battery, and the battery It has excellent cycle stability and has broad application prospects in the field of secondary batteries.

Claims (13)

  1. 一种一体化二次电池，其特征在于，包括一体化电池主体、电池壳体和电解液，所述一体化电池主体包括依次设置的正极、多孔隔膜和负极；所述多孔隔膜包括相对设置的第一表面和第二表面；所述正极包括设置在所述第一表面上的正极活性材料层和设置在所述正极活性材料层上的正极集流体；所述负极设置在所述第二表面上，所述负极包括金属膜层，所述金属膜层同时作为负极集流体和负极活性材料；所述电解液填充于所述正极与所述负极之间。An integrated secondary battery comprising an integrated battery body, a battery case and an electrolyte, the integrated battery body comprising a positive electrode, a porous separator and a negative electrode arranged in sequence; the porous membrane comprising opposite ones a first surface and a second surface; the positive electrode includes a positive active material layer disposed on the first surface and a positive current collector disposed on the positive active material layer; the negative electrode disposed on the second surface The negative electrode includes a metal film layer serving as a negative electrode current collector and a negative electrode active material at the same time; the electrolyte solution is filled between the positive electrode and the negative electrode.
  2. 如权利要求1所述的一体化二次电池，其特征在于，所述金属膜层通过沉积的方式设置在所述第二表面上。The integrated secondary battery according to claim 1, wherein said metal film layer is provided on said second surface by deposition.
  3. 如权利要求1所述的一体化二次电池，其特征在于，所述正极活性材料层通过涂覆的方式设置在所述第一表面上；所述正极集流体通过沉积的方式设置在所述正极活性材料层上。The integrated secondary battery according to claim 1, wherein said positive active material layer is provided on said first surface by coating; said positive current collector is disposed in said manner by deposition On the positive active material layer.
  4. 如权利要求1所述的一体化二次电池，其特征在于，所述金属膜层在其厚度方向上具有三维多孔结构，多孔孔径大小为20nm-100μm。The integrated secondary battery according to claim 1, wherein said metal film layer has a three-dimensional porous structure in a thickness direction thereof, and has a porous pore size of from 20 nm to 100 μm.
  5. 如权利要求1所述的一体化二次电池，其特征在于，所述金属膜层的材质为金属材料，所述金属材料包括铝、铜、铁、锡、锌、镍、锰、钛和铅中的任意一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料。The integrated secondary battery according to claim 1, wherein the metal film layer is made of a metal material, and the metal material comprises aluminum, copper, iron, tin, zinc, nickel, manganese, titanium, and lead. Any one of them, or an alloy containing at least one of the above metal elements, or a composite material containing at least one of the above metal elements.
  6. 如权利要求5所述的一体化二次电池，其特征在于，所述多孔隔膜包括一自所述第二表面向所述多孔隔膜内部延伸形成的混合层，所述混合层的孔洞中附着有所述金属材料，所述混合层的厚度为20nm-10μm。 The integrated secondary battery according to claim 5, wherein said porous separator comprises a mixed layer extending from said second surface toward said porous membrane, said mixed layer having a hole attached thereto The metal material, the mixed layer has a thickness of 20 nm to 10 μm.
  7. 如权利要求1所述的一体化二次电池，其特征在于，所述金属膜层的厚度为0.1μm-300μm。The integrated secondary battery according to claim 1, wherein the metal film layer has a thickness of from 0.1 μm to 300 μm.
  8. 如权利要求1所述的一体化二次电池，其特征在于，所述正极集流体的厚度为0.1μm-300μm，所述正极活性材料层的厚度为10μm-100μm。The integrated secondary battery according to claim 1, wherein the positive electrode current collector has a thickness of from 0.1 μm to 300 μm, and the positive electrode active material layer has a thickness of from 10 μm to 100 μm.
  9. 如权利要求1所述的一体化二次电池，其特征在于，所述正极活性材料包括碳材料、硫化物、氮化物、氧化物、碳化物、以及上述各材料的复合物中的一种或多种。The integrated secondary battery according to claim 1, wherein said positive electrode active material comprises one of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of each of the above materials or A variety.
  10. 如权利要求1所述的一体化二次电池，其特征在于，所述电解液包括电解质和溶剂，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；所述电解液中，所述电解质的浓度为0.1-10mol/L。The integrated secondary battery according to claim 1, wherein said electrolyte comprises an electrolyte and a solvent, and said electrolyte comprises one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt. In the electrolyte, the concentration of the electrolyte is 0.1-10 mol/L.
  11. 一种一体化二次电池的制备方法，其特征在于，包括以下步骤：A method for preparing an integrated secondary battery, comprising the steps of:
    提供多孔隔膜，所述多孔隔膜包括相对设置的第一表面和第二表面；Providing a porous membrane comprising opposing first and second surfaces;
    按一定比例称取正极活性材料，加入适当溶剂充分混合形成均匀浆料；然后将所述浆料均匀涂覆于所述第一表面，得到正极活性材料层，然后在所述正极活性材料层上通过沉积的方式制备正极集流体，形成正极；The positive electrode active material is weighed in a certain ratio, and mixed well by adding a suitable solvent to form a uniform slurry; then the slurry is uniformly coated on the first surface to obtain a positive electrode active material layer, and then on the positive electrode active material layer. Preparing a positive electrode current collector by deposition to form a positive electrode;
    在所述第二表面上沉积金属材料形成金属膜层，得到负极；最终得到一体化电池主体；Depositing a metal material on the second surface to form a metal film layer to obtain a negative electrode; finally obtaining an integrated battery body;
    在惰性气体或无水环境下，然后将所述一体化电池主体装入电池壳体中，加入电解液后封装，得到一体化二次电池。The integrated battery body is then placed in a battery case in an inert gas or waterless environment, and the electrolyte is added and packaged to obtain an integrated secondary battery.
  12. 如权利要求11所述的一体化二次电池的制备方法，其特征在于，所述沉积的方式包括气相沉积、冷喷涂和热喷涂的中一种或多种，所述气相沉积包括物理气相沉积和化学气相沉积中的至少一种。 The method of preparing an integrated secondary battery according to claim 11, wherein the depositing comprises one or more of vapor deposition, cold spray, and thermal spray, and the vapor deposition comprises physical vapor deposition. And at least one of chemical vapor deposition.
  13. 如权利要求11所述的一体化二次电池的制备方法，其特征在于，所述涂覆的方式包括刮涂、旋涂、喷涂、滚涂和挤压涂布中的一种或多种。 The method of preparing an integrated secondary battery according to claim 11, wherein the coating comprises one or more of knife coating, spin coating, spray coating, roll coating, and extrusion coating.
PCT/CN2017/078205 2017-03-24 2017-03-24 Integrated secondary cell, and manufacturing method thereof WO2018170927A1 (en)

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