CN108365173A - Electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof - Google Patents

Electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof Download PDF

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Publication number
CN108365173A
CN108365173A CN201810138814.XA CN201810138814A CN108365173A CN 108365173 A CN108365173 A CN 108365173A CN 201810138814 A CN201810138814 A CN 201810138814A CN 108365173 A CN108365173 A CN 108365173A
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active material
electrode
preparation
electrode active
dry powder
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CN108365173B (en
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夏晖
徐璟
孙硕
昝峰
夏求应
岳继礼
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THE NORTHERN Research Institute OF NJUST
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Northern Research Institute Nanjing University Of Science & Technology
Tianjin Rui Sheng Hui Neng Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof, it is related to secondary battery technology, the preparation method of the electrode for secondary battery, electrode active material dry powder layer is heated using laser, the electrode is obtained after electrode active material dry powder layer melts and solidifies.The magnetically controlled sputter method that the prior art can be alleviated using this method prepares the technical issues of electrode active material layers are slow-growing and existing 3D printing technique causes battery electrical property to decline using binder, achievees the purpose that improve formation efficiency and battery electrical property.

Description

Electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof
Technical field
The present invention relates to secondary battery technologies, more particularly, to a kind of electrode for secondary battery and preparation method thereof and two Primary cell and preparation method thereof.
Background technology
Lithium ion battery has that discharge voltage is high, energy density is high, power density is high, has extended cycle life and memory-less effect Equal many merits, consumer electronics, electric tool, medical electronics, electric vehicle, rail traffic, aerospace, on a large scale can be again The fields such as raw energy access, peak load regulation network frequency modulation and distributed energy storage have a wide range of applications.However, current commercialization lithium battery Using organic liquid electrolyte, inflammable and explosive feature greatly hinders the popularization and application of lithium battery.
With solid electrolyte material develop, there is high working voltage section, safety nonflammable ground solid lithium battery Development will be as saving the key of current lithium battery predicament.However, being limited since the ion in solid electrolyte is in Region, ionic conductivity be far below liquid electrolyte, define the promotion of solid state battery overall performance.Have benefited from semiconductor The development of nanotechnology, the All-solid film batteries for having nanoscale membrane structure become the realization earliest of solid state battery field just Walk the novel lithium battery of industrialization.Future thin film battery is identical as the operation principle of existing lithium battery, and most important difference is electricity There is no organic electrolyte, instead the solid thin-film electrolyte also thinner than the scraps of paper in pond, i.e., on conductive substrates will Each element of battery is sequentially prepared into film according to the sequence of anode, electrolyte, cathode, and finally encapsulation just constitutes a whole electricity Pond can thoroughly solve the security risk of electrolyte leakage.It is had many advantages using the film lithium cell of solid electrolyte, such as： (1) energy density is very big (800Wh/L)；(2) be bent, pierce through still can charge and discharge；(3) in -70 DEG C to 170 DEG C wide temperature ranges It is interior to can be used；(4) year self-discharge rate<3%, it is recycled tens thousand of times；(5) thickness of coordination electrode and electrolyte thin film thickness, can Realize 30C charge and discharge；(6) the big voltage single battery of monomer internal series-connection manufacture 12V or more；(7) with 5V high-field electrode materials Material is matched.In addition, all solid-state thin-film lithium battery also has packaging efficiency higher, the body of idle space in power-supply system can be reduced The features such as product.More it is worth noting that, all solid-state thin-film lithium battery wide operating temperature range makes it can be at aerospace and deep-sea It is worked normally in equal extreme environments, current existing other batteries cannot achieve.All solid-state thin-film lithium battery has excellent Characteristic make its microelectronic device (such as：Smart card, electronic tag, MEMS, integrated circuit), wearable electronic sets The fields such as standby, military, medicine and space flight have wide practical use.
Currently, the preparation of all solid-state thin-film lithium battery is all made of the system of the exploitations such as U.S. Oak Ridge National Laboratory BATES Preparation Method (Solid State Technology 1993,36 (7):59-64), that is, use the method for magnetron sputtering successively in base Anode and electrolyte are deposited on bottom, the method for then using thermal evaporation deposits cathode.It can be obtained using magnetron sputtering preparation method To comparatively dense anode active material layer, but growth rate is relatively low (only a few micrometers per hour).So low growth rate Significantly limit its preparation it is thicker (>The whole volume of the 5um) efficiency of electrode active material layers, battery is restricted, and is also increased Cost prepared by big large-scale production.
Meanwhile using 3D printing technique, printing prepares electrode to some scholars on a current collector, but needed in this method The organic matters such as binder are added in slurry so that the particle in battery active material is bonded together.And the presence of organic matter can be big Width reduces the quality and bulk specific gravity of electrode active material, and burn-up organic matter can form more hole, shape after printing shaping At more crystal boundary and gas-solid interface, it is unfavorable for transmission of the lithium ion in electrode active material, reduces the electrical property of battery.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of electrode for secondary battery, and the second object of the present invention exists In providing a kind of electrode for secondary battery obtained using the preparation method, the magnetically controlled sputter method to alleviate the prior art prepares electricity Pole active material layer is slow-growing and existing 3D printing technique is asked using the technology that binder causes battery electrical property to decline Topic.
The third object of the present invention is to provide a kind of secondary cell including above-mentioned electrode, and the fourth object of the present invention exists In providing a kind of preparation method of secondary cell, to improve the electrical property of secondary cell.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
A kind of preparation method of electrode for secondary battery heats electrode active material dry powder layer using laser, waits for electricity Pole active material dry powder layer melts and obtains the electrode after solidifying.
Further, the electrode active material dry powder layer includes that positive active material dry powder layer or negative electrode active material are dry Bisque；
Preferably, the positive active material be selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, Nickel cobalt lithium aluminate, nickel ion doped, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, lithium fluophosphate, fluorophosphoric acid vanadium lithium, fluorine phosphorus Any one of sour iron lithium, molybdenum oxide or vanadium oxide or at least two combination；
Preferably, the negative electrode active material is selected from graphite, graphene, hard carbon, Si-C composite material, silicon, germanium, tin, two Any one of tin oxide, antimony oxide, lithium titanate, copper oxide, iron oxide or manganese oxide or at least two combination.
Further, the wavelength of the laser is 900-1200nm, and power 6-20W, spot diameter is 40-80 μm；
Preferably, the wavelength of the laser is 1000-1100nm, and power 10-18W, spot diameter is 50-70 μm.
Further, the slurry of electrode active material is coated on collector, is obtained after dry removal solvent described Electrode active material dry powder layer；
Preferably, drying temperature is 100-200 DEG C.
Further, electrode active material is dissolved in solvent, it is polished to obtain the slurry；
Preferably, the solvent is volatile solvent, preferably water or ethyl alcohol.
Further, electrode active material dry powder layer is successively heated using laser, obtains the electrode of multilayered structure Active material dry powder layer；
Preferably, the thickness of every layer of electrode active material dry powder layer is 10-50 microns；
Preferably, the overall thickness of electrode active material dry powder layer is 20-200 microns.
A kind of electrode for secondary battery is obtained according to above-mentioned preparation method.
A kind of secondary cell, including above-mentioned electrode for secondary battery.
A kind of preparation method of secondary cell, be utilized respectively above-mentioned electrode for secondary battery preparation method obtain anode with it is negative Pole, addition electrolyte is assembled to obtain the secondary cell between the anode and the cathode.
Further, the electrolyte is solid electrolyte；
Preferably, solid state electrolysis metallic substance dry powder layer first is prepared in the anode or the negative terminal surface, then using sharp Light heats solid state electrolysis metallic substance dry powder layer, is obtained after solid state electrolysis metallic substance dry powder layer melts and solidifies described solid State electrolyte；
Preferably, the solid state electrolysis metallic substance is selected from Li3aLa(2/3)-aTiO3(0.04<a<0.14)、 Li3+aXaY1-aO4 (X=Si, Sc, Ge, Ti；Y=P, As, V, Cr；0<a<1)、 Li1+aAlaTibGe2-a-b(PO4)3(0<a<1；0≤b<2)、LiZr2 (PO4)3、 Li5La3M2O12(M=Ta, Nb), Li3N-LiX (X=Cl, Br, I), Li9-naMaN2Cl3(M=Na, K, Rb, Cs, Mg、Al；0<a<0.2；0<n<10)、3Li3N-MI (M=Li, Na, K), Li7La3Zr2O12、Li5.5La3Nb1.75In0.25O12、 Li3OCl、Li3OCl0.5Br0.5、 Li10GeP2S12、Li14Zn(GeO4)4、LiPON、LiBH4-LiI、Li2S-MSa(M=Al, Si, P；1<a<3)、Na3PS4、Na3PSe4Or Na3SiS4At least one of.
Compared with the prior art, the present invention has the advantages that：
The preparation method of electrode for secondary battery and solid electrolyte membrane provided by the invention is using laser to electrode activity Substance or solid electrolyte are heated, and can be made in electrode active material or solid electrolyte using the TRANSIENT HIGH TEMPERATURE heating of laser Powder granule melt, after in electrode active material or solid electrolyte powder granule solidification after can make powder granule It is bonded together, to obtain the electrode and solid electrolyte membrane of binder free addition.
The electrode activity of 20-100 micron thickness can be realized in 4-10 minutes using preparation method provided by the invention The preparation of layer or solid electrolyte is a kind of simple and effective, low cost, the new method and new process for being suitble to industrialized production.
Active material in the electrode for secondary battery and solid electrolyte membrane that are obtained using preparation method provided by the invention Filling of the layer without organic matter, therefore the electrode active material and solid-state electrolyte layer consistency that are formed are high, crystal boundary is relatively fewer, more Application suitable for solid state battery.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is standard LiCoO2XRD diagram and the electrode for secondary battery that provides of embodiment 1-3 in LiCoO2Anode is living The XRD diagram of property material layer.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
One aspect of the present invention provides a kind of preparation method of electrode for secondary battery, using laser to electrode activity thing Matter dry powder layer is heated, and the electrode is obtained after electrode active material dry powder layer melts and solidifies.
The preparation method of electrode for secondary battery provided by the invention is heated to electrode active material using laser, The powder granule in electrode active material can be made to melt using the TRANSIENT HIGH TEMPERATURE heating of laser, waited in electrode active material Powder granule can be made to be bonded together after powder granule solidification, to obtain the electrode of binder free addition.
The electrode activity material of 20-100 micron thickness can be realized in 4-10min using preparation method provided by the invention The preparation of the bed of material is a kind of simple and effective, low cost, the new method and new process for being suitble to industrialized production.
It should be noted that in the preparation method of the present invention, electrode activity thing is contained in electrode active material dry powder layer Matter and the inorganic material for contributing to be promoted battery electrical property similar to conductive agent etc., but it is organic not including binder etc. Object.
In certain embodiments of the present invention, the electrode active material dry powder layer includes positive active material dry powder layer Or negative electrode active material dry powder layer.
Preparation method provided by the invention can be suitable for positive active material and negative electrode active material, according to electrode activity The type of substance changes the heating temperature of laser.
In certain embodiments of the present invention, the positive active material is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, phosphorus Sour iron lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, nickel ion doped, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, fluorophosphoric acid Any one of lithium, fluorophosphoric acid vanadium lithium, fluorophosphoric acid iron lithium, molybdenum oxide or vanadium oxide or at least two combination.
In certain embodiments of the present invention, it is multiple to be selected from graphite, graphene, hard carbon, silicon-carbon for the negative electrode active material Any one of condensation material, silicon, germanium, tin, stannic oxide, antimony oxide, lithium titanate, copper oxide, iron oxide or manganese oxide or at least Two kinds of combination.
It is understood that positive active material can carry out routine with cathode negative electrode active material according to the type of battery Selection does not do specific restriction to positive active material or negative electrode active material.
In certain embodiments of the present invention, the wavelength of the laser is 900-1200nm, power 6-20W, hot spot A diameter of 40-80 μm；Still optionally further, the wavelength of the laser is 1000-1100nm, power 10-18W, spot diameter It is 50-70 μm.
Adjust laser wavelength and power so that the heat of laser reaches needed for electrode active material melting temperature, make electrode The edge of the powder granule of active material melts, meanwhile, inside will not melt, when the edge of fusing solidifies again When, powder granule is bonded together, and forms electrode active material layers.The hot spot of laser is set as 40-80 μm can be to electrode The powder granule of active material carries out local heating, temperature-controllable higher.
Wherein, the wavelength of laser it is unrestricted for example can be 900nm, 950nm, 1000nm, 1030nm, 1050nm, 1070nm, 1100nm, 1150nm or 1200nm；The power of laser is unrestricted for example can be：6W、10W、12W、15W、 17W or 20W；The spot diameter of laser for example can be：40 μm, 50 μm, 60 μm, 70 μm or 80 μm.
In certain embodiments of the present invention, electrode active material is heated by 3D laser printers.
Electrode active material dry powder is placed in 3D laser printers, is gradually swept according to the preset path of computer Retouch heating.The powder particle of electrode active material will melt under laser irradiation effect at this time, and it is mutual to be frozen into particle again later Mutually crosslinked electrode active material layers.
In certain embodiments of the present invention, the slurry of electrode active material is coated on collector, is gone through drying Except obtaining the electrode active material dry powder layer after solvent.
Dense uniform can be directly obtained on a current collector by the way that the slurry of electrode active material to be coated on collector Slurry coating, through it is dry remove solvent after can obtain the electrode active material dry powder layer of dense uniform, utilize the coating side Method can also effective coordination electrode active material dry powder layer thickness.
In certain embodiments of the present invention, drying temperature is 100-200 DEG C.Wherein, drying temperature is unrestricted For example, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C or 200 DEG C.
In certain embodiments of the present invention, the material of the collector is in stainless steel, titanium, nickel, aluminium, manganese or molybdenum Any one or at least two combination.
Collector mainly collects the electric current that electrode active material layers generate to form larger current versus Output, therefore collector should come into full contact with electrode active material layers, and as small as possible be preferred is answered in internal resistance.
In certain embodiments of the present invention, electrode active material is dissolved in solvent, it is polished to obtain the slurry Material.Optionally, the solvent is volatile solvent, preferably water or ethyl alcohol.Select volatile solvent drying stage solvent just It can volatilize complete, avoid in laser heating process, solvent volatilizees again impacts the structure of electrode active material layers.
In certain embodiments of the present invention, electrode active material dry powder layer is successively heated using laser, is obtained To the electrode active material dry powder layer of multilayered structure.Optionally, the thickness of every layer of electrode active material dry powder layer is that 10-50 is micro- Rice；Optionally, the overall thickness of electrode active material dry powder layer is 20-200 microns.
The second aspect of the invention provides a kind of electrode for secondary battery, is obtained according to above-mentioned preparation method.
Active material layer filling out without organic matter in the electrode for secondary battery obtained using preparation method provided by the invention It fills, therefore the electrode active material layers consistency formed is high, crystal boundary is relatively fewer, is more suitable for the application of solid state battery.
The third aspect of the invention provides a kind of secondary cell, including above-mentioned electrode for secondary battery.
The second electrode being prepared using electrode for secondary battery provided by the invention has above-mentioned electrode for secondary battery All advantages, details are not described herein.
The fourth aspect of the invention provides a kind of preparation method of above-mentioned secondary cell, is utilized respectively above-mentioned secondary electricity The preparation method of pond electrode obtains positive electrode and negative electrode, and electrolyte, which is added, between the anode and the cathode is assembled to obtain The secondary cell.
It is understood that the second electrode in the present invention can be any type of secondary cell.Wherein, electrolyte can Think liquid electrolyte, or solid electrolyte.When electrolyte is liquid electrolyte, further include in secondary cell have every Film.
In certain embodiments of the present invention, the electrolyte is solid electrolyte.Select solid electrolyte that can have Effect solves the problems, such as that electrolyte is easy burning and explosion.
When electrolyte is solid electrolyte, the method that can also use laser heating prepares solid state electrolysis in electrode surface Matter makes solid electrolyte be contacted more closely with interelectrode.
In certain embodiments of the present invention, first solid state electrolysis metallic substance is prepared in the anode or the negative terminal surface Then dry powder layer heats solid state electrolysis metallic substance dry powder layer using laser, wait for that solid state electrolysis metallic substance dry powder layer melts And obtain the solid electrolyte after solidifying.
In certain embodiments of the present invention, the solid state electrolysis metallic substance is selected from Li3aLa(2/3)-aTiO3(0.04<a <0.14)、Li3+aXaY1-aO4(X=Si, Sc, Ge, Ti；Y=P, As, V, Cr；0<a<1)、Li1+aAlaTibGe2-a-b(PO4)3(0< a<1；0≤b<2)、 LiZr2(PO4)3、Li5La3M2O12(M=Ta, Nb), Li3N-LiX (X=Cl, Br, I), Li9-naMaN2Cl3 (M=Na, K, Rb, Cs, Mg, Al；0<a<0.2；0<n<10)、 3Li3N-MI (M=Li, Na, K), Li7La3Zr2O12、 Li5.5La3Nb1.75In0.25O12、Li3OCl、 Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、LiPON、LiBH4- LiI、 Li2S-MSa(M=Al, Si, P；1<a<3)、Na3PS4、Na3PSe4Or Na3SiS4At least one of.
It is understood that not having excessive restriction in the above embodiment to solid electrolyte, according to secondary cell Type carry out conventional selection.
Below in conjunction with embodiment, the present invention will be further described in detail.
Embodiment 1
The present embodiment is a kind of preparation method of anode of secondary battery, specifically includes following steps：
Step a) prepares slurry：Using water as volatile solvent, micron or nanoscale LiCoO2For positive-active powder Positive-active powder is dissolved in solvent by end, and the slurry of positive active material is made by being sufficiently stirred grinding；
Step b) coating dryings prepare positive active material dry powder layer：Slurry obtained by step a) is coated in using knife coating On collector, control blade coating thickness is in 10 microns；
Wherein collector is aluminium foil, and after scratching slurry, the collector for being coated with slurry is placed in 100-200 DEG C of baking oven Drying, forms the positive active material dry powder layer of dispersion；
The heating of step c) laser prepares anode active material layer：Positive active material dry powder is placed on 3D laser printers In, it is gradually scanned and is heated according to the preset path of computer；LiCoO at this time2Powder will melt under laser irradiation effect It is frozen into particle crosslinked electrode active material layers mutually later, and then obtains anode；
Wherein, when carrying out laser scanning, the wavelength 1070nm of laser, power 10W, hot spot 60um.
Embodiment 2
The present embodiment is a kind of preparation method of anode of secondary battery, compared to the examples, the difference is that, laser Power is different, and the power of laser is 6W in the present embodiment, other and 1 all same of embodiment.
Embodiment 3
The present embodiment is a kind of preparation method of anode of secondary battery, compared to the examples, the difference is that, laser Power is different, and the power of laser is 20W in the present embodiment, other and 1 all same of embodiment.
Fig. 1 shows standard LiCoO2XRD diagram and the electrode for secondary battery that provides of embodiment 1-3 in LiCoO2Anode The XRD diagram of active material layer, it can be seen from the figure that the anode active material layer being prepared using method provided by the invention Do not change LiCoO2Structure.
Embodiment 4
The present embodiment is a kind of preparation method of anode of secondary battery, specifically includes following steps：
Step a) prepares slurry：Using water as volatile solvent, micron or nanoscale LiCoO2For positive-active powder Positive-active powder is dissolved in solvent by end, and the slurry of positive active material is made by being sufficiently stirred grinding；
Step b) coating dryings prepare positive active material dry powder layer：Slurry obtained by step a) is coated in using knife coating On collector, control blade coating thickness is in 20 microns；
Wherein collector is aluminium foil, and after scratching slurry, the collector for being coated with slurry is placed in 100-200 DEG C of baking oven Middle drying forms the positive active material dry powder layer of dispersion；
The heating of step c) laser prepares anode active material layer：Positive active material dry powder is placed on 3D laser printers In, it is gradually scanned and is heated according to the preset path of computer；LiCoO at this time2Powder will melt under laser irradiation effect It is frozen into particle crosslinked electrode active material layers mutually later；
Wherein, when carrying out laser scanning, the wavelength 1070nm of laser, power 10W, hot spot 60um；
Step d) is to obtain the LiCoO of different-thickness2Film repeats step b) and step c), makes pole active material The thickness of layer reaches 60 microns, obtains the anode.
Embodiment 5
The present embodiment is a kind of preparation method of secondary battery negative pole, specifically includes following steps：
Step a) prepares slurry：Using water as volatile solvent, micron or nanoscale graphite are negative electrode active powder, Negative electrode active powder is dissolved in solvent, the slurry of negative electrode active material is made by being sufficiently stirred grinding；
Step b) coating dryings prepare negative electrode active material dry powder layer：Slurry obtained by step a) is coated in using knife coating On collector, control blade coating thickness is in 10 microns；
Wherein collector is aluminium foil, and after scratching slurry, the collector for being coated with slurry is placed in 100-200 DEG C of baking oven Middle drying forms the negative electrode active material dry powder layer of dispersion；
The heating of step c) laser prepares anode active material layer：Negative electrode active material dry powder is placed on 3D laser printers In, it is gradually scanned and is heated according to the preset path of computer；Powdered graphite will melt it under laser irradiation effect at this time After be frozen into particle crosslinked anode active material layer mutually, and then obtain cathode；
Wherein, when carrying out laser scanning, the wavelength 1070nm of laser, power 10W, hot spot 60um.
Embodiment 6
The present embodiment is a kind of preparation method of secondary battery negative pole, compared to the examples, the difference is that, laser Power is different, and the power of laser is 6W in the present embodiment, other and 1 all same of embodiment.
Embodiment 7
The present embodiment is a kind of preparation method of secondary battery negative pole, compared to the examples, the difference is that, laser Power is different, and the power of laser is 20W in the present embodiment, other and 1 all same of embodiment.
Embodiment 8
The present embodiment is a kind of preparation method of secondary cell, is included the following steps：
Step a) prepares slurry：Using water as volatile solvent, micron or nanoscale
Li3aLa(2/3)-aTiO3(0.04<a<0.14) it is electrolyte powder, electrolyte powder is dissolved in solvent, through overcharging Divide agitation grinding that electrolyte slurry is made；
Step b) coating dryings prepare solid state electrolysis metallic substance dry powder layer：By electrolyte slurry obtained by step a) using blade coating Method is coated in the surface of the anode active material layer of 1 gained anode of embodiment, and control blade coating thickness is in 15 microns；
Wherein, collector is aluminium foil, and after scratching slurry, the collector for being coated with slurry is placed in 100-200 DEG C of baking oven Middle drying forms the solid state electrolysis metallic substance dry powder layer of dispersion；
The heating of step c) laser prepares solid-state electrolyte layer：The anode for being coated with solid state electrolysis metallic substance dry powder layer is placed in In 3D laser printers, is gradually scanned and heated according to the preset path of computer；Li at this time3aLa(2/3)-aTiO3(0.04<a <0.14) powder will be frozen into particle crosslinked solid-state electrolyte layer mutually under laser irradiation effect after melting；
Wherein, when carrying out laser scanning, the wavelength 1070nm of laser, power 10W, hot spot 60um；
Step d) secondary cell for assembling：Anode with solid-state electrolyte layer obtained by step c) is provided with embodiment 5 Cathode is assembled, and secondary cell is obtained.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of preparation method of electrode for secondary battery, which is characterized in that carried out to electrode active material dry powder layer using laser Heating, the electrode is obtained after electrode active material dry powder layer melts and solidifies.
2. the preparation method of electrode for secondary battery according to claim 1, which is characterized in that the electrode active material is dry Bisque includes positive active material dry powder layer or negative electrode active material dry powder layer；
Preferably, the positive active material is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt Lithium aluminate, nickel ion doped, iron manganese phosphate for lithium, sulphur, sulfur compound, ferric sulfate lithium, lithium fluophosphate, fluorophosphoric acid vanadium lithium, fluorophosphoric acid iron Any one of lithium, molybdenum oxide or vanadium oxide or at least two combination；
Preferably, the negative electrode active material is selected from graphite, graphene, hard carbon, Si-C composite material, silicon, germanium, tin, titanium dioxide Any one of tin, antimony oxide, lithium titanate, copper oxide, iron oxide or manganese oxide or at least two combination.
3. the preparation method of electrode for secondary battery according to claim 1 or 2, which is characterized in that the wavelength of the laser For 900-1200nm, power 6-20W, spot diameter is 40-80 μm；
Preferably, the wavelength of the laser is 1000-1100nm, and power 10-18W, spot diameter is 50-70 μm.
4. the preparation method of electrode for secondary battery according to claim 1 or 2, which is characterized in that by electrode active material Slurry be coated on collector, through it is dry remove solvent after obtain the electrode active material dry powder layer；
Preferably, drying temperature is 100-200 DEG C.
5. the preparation method of electrode for secondary battery according to claim 1 or 2, which is characterized in that by electrode active material It is dissolved in solvent, it is polished to obtain the slurry；
Preferably, the solvent is volatile solvent, preferably water or ethyl alcohol.
6. the preparation method of electrode for secondary battery according to claim 1 or 2, which is characterized in that using laser to electrode Active material dry powder layer is successively heated, and the electrode active material dry powder layer of multilayered structure is obtained；
Preferably, the thickness of every layer of electrode active material dry powder layer is 10-50 microns；
Preferably, the overall thickness of electrode active material dry powder layer is 20-200 microns.
7. a kind of electrode for secondary battery, which is characterized in that obtained according to claim 1-6 any one of them preparation methods.
8. a kind of secondary cell, which is characterized in that including the electrode for secondary battery described in claim 7.
9. a kind of preparation method of secondary cell, which is characterized in that be utilized respectively claim 1-6 any one of them preparation side Method obtains positive electrode and negative electrode, and electrolyte, which is added, between the anode and the cathode is assembled to obtain the secondary cell.
10. preparation method according to claim 9, which is characterized in that the electrolyte is solid electrolyte；
Preferably, solid state electrolysis metallic substance dry powder layer first is prepared in the anode or the negative terminal surface, then utilizes laser pair Solid state electrolysis metallic substance dry powder layer is heated, and the solid-state electricity is obtained after solid state electrolysis metallic substance dry powder layer melts and solidifies Xie Zhi；
Preferably, the solid state electrolysis metallic substance is selected from Li3aLa(2/3)-aTiO3(0.04<a<0.14)、Li3+aXaY1-aO4(X= Si、Sc、Ge、Ti；Y=P, As, V, Cr；0<a<1)、Li1+aAlaTibGe2-a-b(PO4)3(0<a<1；0≤b<2)、LiZr2 (PO4)3、Li5La3M2O12(M=Ta, Nb), Li3N-LiX (X=Cl, Br, I), Li9-naMaN2Cl3(M=Na, K, Rb, Cs, Mg, Al；0<a<0.2；0<n<10)、3Li3N-MI (M=Li, Na, K), Li7La3Zr2O12、Li5.5La3Nb1.75In0.25O12、Li3OCl、 Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、LiPON、LiBH4-LiI、Li2S-MSa(M=Al, Si, P；1<a< 3)、Na3PS4、Na3PSe4Or Na3SiS4At least one of.
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CN109830741A (en) * 2019-01-28 2019-05-31 蜂巢能源科技有限公司 Sulfenyl richness lithium solid electrolyte and its preparation method and application
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CN113594552A (en) * 2021-08-05 2021-11-02 郑州中科新兴产业技术研究院 Preparation method of all-solid-state battery unit
CN114583283A (en) * 2021-12-28 2022-06-03 上海瑞浦青创新能源有限公司 Method for manufacturing solid-state battery by using 3D printing technology

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