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WO2018170927A1 - Accumulateur intégré et son procédé de fabrication - Google Patents

Accumulateur intégré et son procédé de fabrication 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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Prior art keywords
positive electrode
active material
secondary battery
integrated
current collector
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PCT/CN2017/078205
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English (en)
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/fr
Publication of WO2018170927A1 publication Critical patent/WO2018170927A1/fr

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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.

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  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention concerne un accumulateur intégré comprenant un corps principal intégré, un bac d'accumulateur et une solution électrolytique. Le corps principal intégré comprend une électrode positive, une membrane de séparateur poreuse (02) et une électrode négative (01) agencées séquentiellement. La membrane de séprateur poreuse (02) comprend une première surface et une seconde surface agencées de manière opposée. L'électrode positive comprend une couche de matériau actif d'électrode positive (03) disposée sur la première surface, et un collecteur de courant d'électrode positive (04) disposé sur la couche de matériau actif d'électrode positive (03). L'électrode négative (01) est disposée sur la seconde surface et comprend une couche de type film métallique servant de collecteur de courant d'électrode négative et de matériau actif d'électrode négative en même temps. La solution électrolytique est remplie entre l'électrode positive et l'électrode négative (01). De par l'agencement direct du collecteur de courant d'électrode positive (04) sur la surface du matériau actif d'électrode positive, cet accumulateur intégré permet au collecteur de courant d'électrode positive (04) d'être en bon contact avec le matériau actif d'électrode positive, réduisant ainsi efficacement une résistance de contact de l'accumulateur, et en conséquence améliorant la capacité de débit. De plus, cet accumulateur intégré est de structure simple. La présente invention concerne également un procédé de fabrication de l'accumulateur intégré.
PCT/CN2017/078205 2017-03-24 2017-03-24 Accumulateur intégré et son procédé de fabrication WO2018170927A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103545533A (zh) * 2013-10-18 2014-01-29 中国第一汽车股份有限公司 一种高比能量的锂电池及锂电池的集流体制备方法
CN105449186A (zh) * 2015-11-18 2016-03-30 中国科学院深圳先进技术研究院 一种新型二次电池及其制备方法
CN105529492A (zh) * 2015-12-09 2016-04-27 江苏科技大学 一种负极为纯铝的二次离子电池及制备方法
CN105826517A (zh) * 2016-06-13 2016-08-03 周虎 一种碳膜锂离子电池负极及生产方法
CN106299237A (zh) * 2016-09-27 2017-01-04 柔电（武汉）科技有限公司 自支撑极片及其制备方法、电池及其电芯

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103545533A (zh) * 2013-10-18 2014-01-29 中国第一汽车股份有限公司 一种高比能量的锂电池及锂电池的集流体制备方法
CN105449186A (zh) * 2015-11-18 2016-03-30 中国科学院深圳先进技术研究院 一种新型二次电池及其制备方法
CN105529492A (zh) * 2015-12-09 2016-04-27 江苏科技大学 一种负极为纯铝的二次离子电池及制备方法
CN105826517A (zh) * 2016-06-13 2016-08-03 周虎 一种碳膜锂离子电池负极及生产方法
CN106299237A (zh) * 2016-09-27 2017-01-04 柔电（武汉）科技有限公司 自支撑极片及其制备方法、电池及其电芯

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