CN103730630A - Combined electrode of battery and preparation method thereof - Google Patents

Combined electrode of battery and preparation method thereof Download PDF

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Publication number
CN103730630A
CN103730630A CN201310726380.2A CN201310726380A CN103730630A CN 103730630 A CN103730630 A CN 103730630A CN 201310726380 A CN201310726380 A CN 201310726380A CN 103730630 A CN103730630 A CN 103730630A
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solid electrolyte
combination electrode
carbon nano
ion battery
electrode
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吴忠振
潘锋
范浩森
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The application relates to the field of energy storage materials, and discloses a combined electrode with ultrahigh electron and ionic conductivity and a preparation method thereof. The combined electrode is formed in a manner that a battery active material is uniformly tied in a three-dimensional multi-hole network formed by carbon nano tubes which are connected in a crossing manner, and meshes and the surface of the active material are filled or coated with a solid electrolyte material. According to the combined electrode, the carbon nano tubes, which are communicated with one another, can form an ultrahigh electrical transmission network, on the one hand, a solid electrolyte can provide the ultrahigh lithium-ion transmission capacity while not influencing the connection of the carbon nano tubes and the conductive capacity of the electrode; on the other hand, the three-dimensional network formed by the carbon nano tubes is also fixed by virtue of the solid electrolyte, the formation of a solid electrolyte interface is controlled, and an active material is protected under the high charge-discharge voltage. The combined electrode has the high reversible capacity and the enhanced rate capability, and can meet the requirement of a power automobile or a mixed power automobile.

Description

A kind of combination electrode and preparation method thereof for battery
Technical field
The application relates to field of batteries, combination electrode that particularly a kind of battery is used and preparation method thereof.
Background technology
Energy problem is the Vital Strategic Problems of 21st century, and the development in the fields such as new forms of energy equipment and power vehicle has proposed more harsh requirement to energy storage.At present, the progress in energy storage field mainly depends on the development of battery technology, and in battery technology, the performances such as the capacity of positive and negative pole material, multiplying power, safety play a crucial role.
To be widely used in real-life lithium ion battery as example, its electrode General Requirements can either be by electric transmission in all active material particles, lithium ion can be delivered to rapidly in all active materials again, be that electrode requirement had both had high electronic conductivity, needing again has higher ionic conductivity.But, most for the non-constant of lithium ion battery plus-negative plate material electronics conductivity at present, cause active material reaction inhomogeneous, form polarity effect, high rate performance reduces greatly.At present, can only adopt the form of film, or preparation nanostructure, and add the increase conductivity such as conductive black, still, to improving energy content of battery density, cause larger restriction like this.
In order to improve the monolithic conductive of electrode, the carbon nanomaterial of some highly electron conductives, as carbon nano-tube, Graphene etc., is used to and active material composition combination electrode, has greatly improved the electronic conductivity of electrode.But the materials such as the conductive black adding in electrode, binding agent are coated on around active material, still affect the transmission of electronics and ion.
Summary of the invention
Battery combination electrode providing a kind of architecture advances and preparation method thereof is provided the application's object.
To achieve these goals, the technical scheme that the application adopts is as follows:
The application discloses a kind of battery combination electrode, wherein the active material of combination electrode is evenly strapped in the three-dimensional porous network being formed by carbon nano-tube interconnection, in the hole forming in three-dimensional network and surface of active material fill or be coated solid electrolyte material, form combination electrode.It should be noted that, the application provides a kind of combination electrode of architecture advances, and the combination electrode of this structure can be for the battery of existing all kinds, various model, various forms on market; And wherein active material can be for positive electrode active materials be to make the positive pole of battery, also negative active core-shell material to make battery cathode.
In the application's combination electrode, carbon nano-tube can be used the carbon nano-tube of existing various structures, is preferably selected from but is not limited only at least one in nanofiber that nanotube that Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, functionalized carbon nano-tube, electric conducting material form, nanometer rods that electric conducting material forms or electric conducting material form.
Wherein, preferred electric conducting material is selected from least one in the Inorganic Non-metallic Materials of metal material, conduction or the high-molecular organic material of conduction.
In the application, metal material is selected from one or several in copper, nickel, zinc, tin, magnesium, aluminium, manganese, chromium, cadmium, tellurium, indium, antimony, titanium, gold, platinum, molybdenum and silver; The Inorganic Non-metallic Materials of conduction is selected from carbon, zinc oxide aluminum, tin indium oxide, mixes one or several in the tin oxide of fluorine and the composite material of their alloy or composition; The high-molecular organic material of conduction is selected from one or several in polyaniline, polythiophene, polypyrrole, polyphenylacetylene, polyacetylene, polyhenylene, polyphenylene sulfide, fullerene and their derivative.
In the application's combination electrode, solid electrolyte material is selected from one or more in inorganic solid electrolyte, organic polymer solid electrolyte, inorganic organic composite solid electrolyte or solid-liquid composite solid electrolyte; Or solid-liquid composite solid electrolyte is the solid-liquid composite polymeric solid electrolyte that one or more and the liquid electrolyte in inorganic solid electrolyte, organic polymer solid electrolyte, inorganic organic composite solid electrolyte is combined to form; In the application, the concrete form of solid electrolyte material is solid-state version, colloid type or porous type.
Preferably, inorganic solid electrolyte is selected from Al 2o 3, TiO 2, at least one in ZnO, SnO, RuO, LiPON, Li-V-Si-O series, Li-P-S series, Li-Ge-P-S series, Li-Sn-S series, Li-As-Sn-S series, Li-La-Zr-O series or Li-La-Ti-O series; Organic polymer solid electrolyte is solid-state version or the colloid type solid polyelectrolyte that polymeric matrix or polymeric matrix and lithium salts are combined to form, polymeric matrix is selected from least one in PEO, PPO, PAN, PVC, PVDC, PMMA or PVdF-HVP, and lithium salts is selected from LiClO 4, LiPF 6, LiBF 4, LiAsF 6or LiCF 3sO 3in at least one; Inorganic organic composite solid electrolyte is in organic polymer solid electrolyte, to add inorganic solid electrolyte, Mg (ClO 4) 2, La 0.55li 0.35tiO 2, BaTiO 3or γ-LiAlO 2in at least one powder form; In solid-liquid composite polymeric solid electrolyte, liquid electrolyte is selected from EC, DEC, DMC, FEC, EMC, D 2, HfiP, LiPF 6or LiBF 4in one or more.
In the application's combination electrode, active material is selected from least one in anode material for lithium-ion batteries or negative material, sodium-ion battery positive electrode or negative material, anode of magnesium ion battery material or negative material, aluminium ion cell positive material or negative material; Wherein, anode material for lithium-ion batteries is selected from LiMnO 2, LiNiO 2, LiCoO 2, LiMn 2o 4, LiM xk yn 1-x-yo 2, Li 1-zna zni xco ymn 1-x-yo 2, Li 2mnO 3, Li 2ru 1 – ymn yo 3, xLi 2mnO 3(1-x) LiMO 2, LiMXO 4, S, Li xs, M xv 2o 5, MoO 3-x, MS xo yin at least one; LiM xk yn 1-x-yo 2in M, K, N be not independently selected from the one in Fe, Mn, Ni, Co, V, Ti, Cu, Zn, Y, Zr, Nb, Mo, Te, Ru, Rh, Sb, Ag, Cd, La, Ta, W, Pt, Au or Cr, wherein independently be not selected from and refer to, M, K, N three are not identical, M has selected one of them element, K, N just can only select remaining other element, 0≤x≤1,0≤y≤1; Li 1-zna zni xco ymn 1-x-yo 2in 0≤x≤1; 0≤y≤1; 0≤z≤1; Li 2ru 1 – ymn yo 3in 0≤y≤1; xLi 2mnO 3(1-x) LiMO 2in 0≤x≤0.5, M is Ni, Mn or Co; LiMXO 4in M be Fe, Mn, Ni, Co, V, Ti or Cr, X is Si, P or S; Li x0≤x≤8 in S; M xv 2o 5in M be Ag, Ni or Cu, 0≤x≤1; MoO 3-xand MS xo ymiddle M is Mo, Fe or W, 0≤x≤2,0≤y≤2; Lithium ion battery negative material is selected from least one in Li, C, Si, Sn or Ge, or the alloy of at least one in Li, C, Si, Sn or Ge, or the oxide of at least one in Li, C, Si, Sn or Ge or nitride, or described lithium ion battery negative material is M xa y, wherein M is Ti, V, Fe, Ni, Co, Mn, Cu, Cr or Zn, A is O or N, 1≤x≤3,1≤y≤5; Sodium-ion battery positive electrode is selected from Na xk ymO 2, Na zm xk yn 1-x-yo 2, NaMXO 4, Na xmS y, M xv 2o 5, MoO 3-x, Na xwO 3-yin at least one; Na xy ymO 2in M be Mn, Ni or Co, Y is Li, K or Rb, x+y<1; Na zm xk yn 1-x-yo 2in M be Fe, Mn, Ni, Co, V, Ti or Cr, 0≤x≤1,0≤y≤1, z<1; NaMXO 4in M be Fe, Mn, Ni, Co, V, Ti or Cr, X is Si, P or S; Na xmS yin M be Ti, Nb, Ta, Mo, Cr, V or W, 0<x<2,1≤y≤3; M xv 2o 5in M be Ag, Ni or Cu, 0≤x≤1; MoO 3-xand Na xwO 3-ymiddle 0<x<2,0≤y≤1; Anode material of lithium-ion battery is selected from least one in binary or the ternary alloy three-partalloy of Na, C or Na and Pb, Sn, Bi, Ga, Ce, Si composition; Anode of magnesium ion battery material is selected from Mo 6t 8, Mo 6s xse y, MgMnO 3, MgFeSiO 4, MgTi 2o 5, Cu 0.1doped VO x, S, SMn doped V 2o 5, at least one in DMcT-PAn/Mg, CMS-Pan/Mg, PDTDA/Mg; Mo 6t 8middle T is S or Se; Mo 6s xse ymiddle x+y=8; Magnesium ion battery negative material is selected from least one in Mg metal and alloy thereof; Aluminium ion cell positive material can be MnO 2, Mn 2o 4, AlMn 2o 4, Ti (AlCl 4) 2, MnCl (AlCl 4), Co (AlCl 4) 2, V 2o 5, at least one; Aluminium ion cell negative electrode material is at least one in Al or Al alloy.
The application's another side also discloses the application of combination electrode in lithium ion battery, sodium-ion battery, Magnesium ion battery or aluminium ion battery.It should be noted that, the application's combination electrode can be for existing various batteries, comprise lithium ion battery, sodium-ion battery, Magnesium ion battery and aluminium ion battery, and can be for the lithium ion battery of shell-type battery, soft-package battery and the special shape of all size or purposes, sodium-ion battery, Magnesium ion battery or aluminium ion battery.
The application's another side also discloses the preparation method of the application's combination electrode, comprises the following steps:
A. carbon nano-tube and active material are uniformly dispersed;
In a kind of implementation of the application, be to weigh a certain amount of active material powder with digital calculation balance, pour in the deionized water that adds surfactant, add carbon nano-tube simultaneously, be placed on common ultrasonic 2-10min on ultrasonic cell disrupte machine equipment, fully to mix dispersion.
B. finely dispersed carbon nano-tube and active material compound are prepared into the film with three-dimensional porous network configuration;
In the application's execution mode, preferably adopt vacuum filtration method or natural sediment method to be prepared into three-dimensional porous network thin-film, wherein, the device of vacuum filtration method as shown in Figure 1, by surge flask 1, bottle,suction 4, vacuum pump 5, exhaust tube 6 clips 7 form, between surge flask 1 and bottle,suction 4, add aluminium oxide masterplate or PVDF filter membrane 2 and filter paper 3, the steps include: vacuum filtration device to connect by Fig. 1 structure, ultrasonic scattered solution is poured in surge flask 1, open vacuum pump 5 and start suction filtration, after treating that solution is drained, add a small amount of solvent clean, film forms on aluminium oxide masterplate, finally the aluminium oxide masterplate of laminated film that has deposited tertiary cathode material and conducting metal rod being put into baking oven dries, 100 ℃ of temperature, film can come off from aluminium oxide masterplate after drying automatically,
C. solid electrolyte is coated in three-dimensional porous network and on film surface, forms combination electrode;
In the application's execution mode, adopt Vacuum Coating method, cladding process or soak solidification method solid electrolyte is coated in three-dimensional porous network and on film surface; Wherein, Vacuum Coating method is that solid electrolyte is deposited on three-dimensional network electrode by vacuum evaporation or magnetron sputtering method, and forms coated combination electrode continuously on mesh neutralized film surface; Cladding process is by the inorganic solid electrolyte powder of slurry state, or liquid solid polyelectrolyte or its presoma are coated in three-dimensional porous network thin-film surface, dry and form the continuous coated combination electrode of solid electrolyte again, during coating, liquid automatic infiltration enters in mesh active material is coated; Soaking solidification method is the inorganic solid electrolyte powder that three-dimensional network electrode is immersed in to slurry state, or in the solid polyelectrolyte of liquid state or the coating of its presoma, formation is coated rear taking-up continuously, then oven dry forms combination electrode.
Owing to adopting above technical scheme, the application's beneficial effect is:
The application's combination electrode is coated on active material in the three dimensional network pore structure of carbon nano-tube formation, utilizes carbon nano tube network to carry out the transmission of electronics and ion, not only can greatly improve electronic conductivity and the ionic conductivity of electrode, improves its high rate performance; Can make electrolyte osmosis arrive around each ternary material particle simultaneously, make all particles separate lithium simultaneously, thereby avoided part surface particle excessive and change spinel structure into by layer structure owing to separating lithium, also avoided the reversible capacity causing thus significantly to decline.The application's combination electrode, the reversible capacity of the ternary material electrode that its reversible capability of charging and discharging is prepared far above conventional method; The reversible capacity of the application's combination electrode approaches the theoretical capacity that even can reach ternary material.
Accompanying drawing explanation
Fig. 1 is vacuum filtration device schematic diagram, and 1 is that surge flask, 2 is that aluminium oxide masterplate or PVDF filter membrane, 3 are that filter paper, 4 is that bottle,suction, 5 is that vacuum pump, 6 is that exhaust tube, 7 is clip;
Fig. 2 is the application's composite construction schematic diagram, and wherein 21 is active material, and 22 is carbon nano-tube, and 23 is solid electrolyte material;
Fig. 3 is based on Li (Ni in the embodiment of the present application 0.5co 0.2mn 0.3) O 2combination electrode stereoscan photograph, be (a) that solid electrolyte is filled the scanned photograph before coated, (b) for solid electrolyte is filled the scanned photograph after being coated;
Fig. 4 is based on Li (Ni in the embodiment of the present application 0.5co 0.2mn 0.3) O 2combination electrode and conventional electrode coated electrochemistry performance contrast, (a) be front 4 charging and discharging curves, (b) be high rate performance test curve; (a) in, three curves of 1st cycle indication are from left to right sequentially the test curve of comparative example one, comparative example two and embodiment bis-, and three curves of 4th cycle indication are from left to right sequentially the test curve of comparative example one, comparative example two and embodiment bis-; (b) in, be sequentially from top to bottom the test curve of embodiment bis-, comparative example two, comparative example one.
Embodiment
Although there is the research that carbon nano-tube is joined in active material to the electronic conductivity to improve electrode in prior art, but, because the materials such as the conductive black adding in electrode, bonding agent have affected electronics and the ion transfer of electrode greatly, therefore the improvement effect that, adds carbon nano-tube is also received impact accordingly.The application is just under such background, creationary carbon nano-tube is made to three-dimensional porous network configuration, take this structure as shaping carrier, active material is strapped in wherein uniformly, use carbon black and bonding agent have been avoided, adopt solid electrolyte material to be coated on surface of active material, form firm combined electrode structure; The carbon nano-tube being interconnected forms the electric transmission network of superelevation, and solid electrolyte can provide the lithium ion transmittability of superelevation on the one hand, can not affect the connection of carbon nano-tube simultaneously, can not affect the conductive capability of electrode; The existence of solid electrolyte on the other hand; the three-dimensional network that all right fixed carbon nanotube forms; control the formation of solid electrolyte interface; and can under higher charging/discharging voltage, there is protective effect to active material; whole combination electrode utilizes carbon nano tube network to carry out the transmission of electronics and ion; with only directly add the mode of carbon nano-tube in active material compared with, the application has improved electronic conductivity greatly.
It should be noted that, the application's an important inventive concept is the structure of combination electrode, therefore, no matter is positive electrode active materials or negative active core-shell material, can be applicable to the application; Meanwhile, the carbon nano-tube of various structures of the prior art, model or function, the solid electrolyte material of various formulas also may be used to the application, all in the application's protection range; And be not limited only to the application record positive electrode active materials, negative active core-shell material, carbon nano-tube and solid electrolyte material.
Below by specific embodiment, also by reference to the accompanying drawings the application is described in further detail.Following examples are only further described the application, should not be construed as the restriction to the application.
The preparation of embodiment mono-combination electrode
The preparation method of combination electrode comprises the following steps:
A. carbon nano-tube and active material are uniformly dispersed.
Weigh a certain amount of reactive powder material with digital calculation balance, pour in the deionized water that adds surfactant, add carbon nano-tube simultaneously, be placed on common ultrasonic 2-10min on ultrasonic cell disrupte machine equipment.
B. carbon nano-tube and active material are prepared into the film with three-dimensional porous network configuration.
This step can be used the one in vacuum filtration method or natural sediment method.
The device of vacuum filtration method as shown in Figure 1, is comprised of surge flask 1, bottle,suction 4, vacuum pump 5, exhaust tube 6 and clip 7, adds aluminium oxide masterplate or PVDF filter membrane 2 and filter paper 3 between surge flask 1 and bottle,suction 4.The steps include: vacuum filtration device to connect by Fig. 1 structure, ultrasonic scattered solution is poured in surge flask 1, open vacuum pump 5 and start suction filtration, after treating that solution is drained, add a small amount of solvent clean, film forms on aluminium oxide masterplate, finally the aluminium oxide masterplate of laminated film that has deposited tertiary cathode material and conducting metal rod is put into baking oven and dries, 100 ℃ of temperature, film can come off from aluminium oxide masterplate after drying automatically.
Natural sediment method is that scattered solution is poured in flat bottom beaker, liquid is dried naturally or heat evaporate to dryness, obtains the three-dimensional network film of natural sediment.
Because active material and carbon nano-tube are homodisperse, therefore, carbon nano-tube self-assembling formation three dimensional network pore structure, and active material is naturally bound in mesh.
C. solid electrolyte is coated in three-dimensional network electrode and on surface.
This step can be used Vacuum Coating method, cladding process, soaks solidification method or is coated the one in method by the SEI layer forming in circulating battery process.
Vacuum Coating method, is that solid electrolyte is deposited on three-dimensional network electrode by vacuum evaporation or magnetron sputtering method, and forms coated combination electrode continuously with surface therein.
Cladding process, be will slurry state inorganic solid electrolyte powder, or liquid solid polyelectrolyte or its presoma be coated in three-dimensional network electrode and surface, then dry and form the continuous coated combination electrode of solid electrolyte.
Soaking solidification method is the inorganic solid electrolyte powder that three-dimensional network electrode is immersed in to slurry state, or in the solid polyelectrolyte of liquid state or the coating of its presoma, formation is coated rear taking-up continuously, then oven dry forms combination electrode.
By the coated method of SEI layer forming in circulating battery process, to have the three-dimensional mesh film of carbon nano-tube of active material to be directly made into after battery the good constraint of suction filtration, pass through charge and discharge cycles, on the network of active material and carbon nano-tube, form SEI coated, SEI has ionic conduction ability, also can form the coating layer of solid electrolyte.
Embodiment bis-is by Li (Ni 0.5co 0.2mn 0.3) O 2the shell-type lithium ion half-cell of/CNT/SEI composition combination electrode
The preparation of combination electrode: adopt the method in embodiment mono-, with Li (Ni 0.5co 0.2mn 0.3) O 2for active material, Single Walled Carbon Nanotube is as conductive network, and vacuum filtration method forms the positive pole of three-dimensional conductive network, cuts into the disk of 3/8 inch of diameter, forms 2032 shell-type half-cells with barrier film, lithium sheet.By charge and discharge cycles for the first time, in three-dimensional network and the SEI layer of the coated one deck macroion conductance of surface of active material, form the combination electrode described in the application.
In this example, prepared combined electrode structure schematic diagram as shown in Figure 2, stereoscan photograph before coated solid electrolyte is as Fig. 3 a, form solid electrolyte coated after a charge and discharge cycles after, stereoscan photograph is as Fig. 3 b, in this example, half-cell has obtained higher reversible capacity, the high rate performance of enhancing, as shown in Figure 4.
Embodiment tri-is by Li (Ni 0.5co 0.2mn 0.3) O 2the shell-type lithium ion half-cell of/CNT/LiPON composition combination electrode
The preparation of combination electrode: adopt the method in embodiment mono-to use Li (Ni 0.5co 0.2mn 0.3) O 2for active material, Single Walled Carbon Nanotube is as conductive network, vacuum filtration method forms the positive pole of three-dimensional conductive network, the coated LiPON solid electrolyte of radio-frequency magnetron sputter method preparation, sputtering parameter is: radio-frequency power 40-80W, operating air pressure 1-2Pa, working gas high pure nitrogen, sputtering time 20-60min.
Battery preparation: the combination electrode preparing is cut into the disk of 3/8 inch of diameter, form 2032 shell-type half-cells with barrier film, lithium sheet.
Combined electrode structure prepared in this example is identical with execution mode two, experiment test demonstration, and this routine half-cell has obtained higher reversible capacity and the high rate performance of enhancing.
Embodiment tetra-is by Li (Ni 0.5co 0.2mn 0.3) O 2/ CNT/Li 10geP 2s 12the shell-type lithium ion half-cell of composition combination electrode
The preparation of combination electrode: adopt the method in embodiment mono-to use Li (Ni 0.5co 0.2mn 0.3) O 2for active material, Single Walled Carbon Nanotube is as conductive network, and vacuum filtration method forms the positive pole of three-dimensional conductive network.By the Li of preparation 10geP 2s 12powder is put into nmp solution, can suitably dissolve the PVDF of 2-5%, uniform stirring form slurry in NMP.Three-dimensional network electrode is placed on rotation platform, and a upper 1-2 drips Li 10geP 2s 12slurry, rotation is until slurry is evenly being paved with whole electrode, rotating speed 50-100r/min.
Battery preparation: the combination electrode preparing is cut into the disk of 3/8 inch of diameter, form 2032 shell-type half-cells with barrier film, lithium sheet.
Combined electrode structure prepared in this example is identical with execution mode two, test result demonstration, and the reversible capacity of this routine half-cell and high rate performance all strengthen to some extent.
Embodiment five is by Li (Ni 0.5co 0.2mn 0.3) O 2/ CNT/PEO-LiClO 4the shell-type lithium ion half-cell of composition combination electrode
The preparation of combination electrode: adopt the method in embodiment mono-to use Li (Ni 0.5co 0.2mn 0.3) O 2for active material, Single Walled Carbon Nanotube is as conductive network, and vacuum filtration method forms the positive pole of three-dimensional conductive network.LiClO 4in vacuum drying chamber, 180 ℃ of vacuum drying treatment 12h are to remove the crystallization water, and polyethylene glycol oxide is 50 ℃ of vacuum drying treatment 12h in vacuum drying chamber, acetonitrile, ethylene carbonate, propene carbonate is respectively through second distillation processing, in nitrogen glove box, and the LiClO of metering 4, polyethylene glycol oxide powder, ethylene carbonate and (or) propene carbonate join in the conical flask that 150ml acetonitrile solvent is housed, and through fully stirring, makes LiClO 4form even complex compound with polyethylene glycol oxide and fully mix with plasticizer, three-dimensional conductive network good suction filtration is soaked as in solution, and taking out fast, being clipped on two blocks of clean sheet glass, being cooled to room temperature, forming the combination electrode described in the application.
Battery preparation: the combination electrode preparing is cut into the disk of 3/8 inch of diameter, form 2032 shell-type half-cells with barrier film, lithium sheet.
Combined electrode structure prepared in this example is identical with execution mode two, and compared with the half-cell of preparing with conventional method, this routine half-cell has obtained higher reversible capacity and the high rate performance of enhancing.
Embodiment six is by Li (Ni 0.5co 0.2mn 0.3) O 2/ CNT/PEO-LiClO 4other form lithium ion batteries of composition combination electrode
The preparation of combination electrode: adopt the method in embodiment mono-and two or three, four, five to prepare combination electrode.
Battery preparation: the combination electrode preparing is cut into the sheet of arbitrary dimension or shape, with barrier film, lithium sheet or other negative materials composition lithium ion half-cell Soft Roll or other special shapes and packaged form or full battery.
Combined electrode structure prepared in this example is identical with execution mode two, and in this example, half-cell has obtained higher reversible capacity and the high rate performance of enhancing.
Comparative example one
This comparative example adopts active material and the electrolyte identical with embodiment bis-, and its difference is only, does not use carbon nano-tube, adds carbon black and bonding agent in active material, with conventional painting method, is prepared into traditional electrode, then prepares half-cell and tests.
Shown in test result Fig. 4, its reversible capacity of electrode prepared by conventional method is all relative poor with high rate performance.
Comparative example two
This comparative example adopts the materials and methods identical with comparative example one to prepare electrode, adopts conventional coating to prepare electrode, and difference is in electrode, with 5% carbon nano-tube, to have substituted the carbon black of equivalent amount.It should be noted that, the carbon nano-tube of adding in this comparative example is directly to add in electrode, does not prepare carbon nano-tube three dimensional network pore membrane, therefore, has yet added carbon black and bonding agent in active material simultaneously.Electrode and the half-cell of preparation adopt identical method to test.
Shown in test result Fig. 4, although reversible capacity and the high rate performance of the electrode of this example preparation comparative example one is made moderate progress,, compared with the application's combination electrode, the reversible capacity of electrode and high rate performance or poor.
Above content is the further description of the application being done in conjunction with concrete execution mode, can not assert that the application's concrete enforcement is confined to these explanations.For the application person of an ordinary skill in the technical field, not departing under the prerequisite of the application's design, can also make some simple deduction or replace, all should be considered as belonging to the application's protection range.

Claims (10)

1. a battery combination electrode, it is characterized in that: the active material of described combination electrode is evenly strapped in the three-dimensional porous network being formed by carbon nano-tube interconnection, in the hole forming in three-dimensional network and surface of active material fill or be coated solid electrolyte material, form combination electrode.
2. combination electrode according to claim 1, is characterized in that: described carbon nano-tube is selected from least one in the nanofiber that nanotube that Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes, functionalized carbon nano-tube, electric conducting material form, nanometer rods that electric conducting material forms or electric conducting material form.
3. combination electrode according to claim 2, is characterized in that: described electric conducting material is selected from least one in the Inorganic Non-metallic Materials of metal material, conduction or the high-molecular organic material of conduction.
4. combination electrode according to claim 3, is characterized in that: described metal material is selected from one or several in copper, nickel, zinc, tin, magnesium, aluminium, manganese, chromium, cadmium, tellurium, indium, antimony, titanium, gold, platinum, molybdenum and silver; The Inorganic Non-metallic Materials of described conduction is selected from carbon, zinc oxide aluminum, tin indium oxide, mix one or several in the tin oxide of fluorine and the composite material of their alloy or composition; The high-molecular organic material of described conduction is selected from one or several in polyaniline, polythiophene, polypyrrole, polyphenylacetylene, polyacetylene, polyhenylene, polyphenylene sulfide, fullerene and their derivative.
5. combination electrode according to claim 1, is characterized in that: described solid electrolyte material is selected from one or more in inorganic solid electrolyte, organic polymer solid electrolyte, inorganic organic composite solid electrolyte or solid-liquid composite solid electrolyte; Or described solid-liquid composite solid electrolyte is the solid-liquid composite polymeric solid electrolyte that one or more and the liquid electrolyte in described inorganic solid electrolyte, described organic polymer solid electrolyte, described inorganic organic composite solid electrolyte is combined to form; The concrete form of described solid electrolyte material is solid-state version, colloid type or porous type.
6. combination electrode according to claim 5, is characterized in that: described inorganic solid electrolyte is selected from Al 2o 3, TiO 2, at least one in ZnO, SnO, RuO, LiPON, Li-V-Si-O series, Li-P-S series, Li-Ge-P-S series, Li-Sn-S series, Li-As-Sn-S series, Li-La-Zr-O series or Li-La-Ti-O series;
Described organic polymer solid electrolyte is solid-state version or the colloid type solid polyelectrolyte that polymeric matrix or polymeric matrix and lithium salts are combined to form, described polymeric matrix is selected from least one in PEO, PPO, PAN, PVC, PVDC, PMMA or PVdF-HVP, and described lithium salts is selected from LiClO 4, LiPF 6, LiBF 4, LiAsF 6or LiCF 3sO 3in at least one;
Described inorganic organic composite solid electrolyte is in described organic polymer solid electrolyte, to add inorganic solid electrolyte, Mg (ClO 4) 2, La 0.55li 0.35tiO 2, BaTiO 3or γ-LiAlO 2in at least one powder form;
Liquid electrolyte in described solid-liquid composite polymeric solid electrolyte is selected from EC, DEC, DMC, FEC, EMC, D 2, HfiP, LiPF 6or LiBF 4in one or more.
7. combination electrode according to claim 1, is characterized in that: described active material is selected from least one in anode material for lithium-ion batteries or negative material, sodium-ion battery positive electrode or negative material, anode of magnesium ion battery material or negative material, aluminium ion cell positive material or negative material;
Described anode material for lithium-ion batteries is selected from LiMnO 2, LiNiO 2, LiCoO 2, LiMn 2o 4, LiM xk yn 1-x-yo 2, Li 1-zna zni xco ymn 1-x-yo 2, Li 2mnO 3, Li 2ru 1 – ymn yo 3, xLi 2mnO 3(1-x) LiMO 2, LiMXO 4, S, Li xs, M xv 2o 5, MoO 3-x, MS xo yin at least one;
LiM xk yn 1-x-yo 2in M, K, N be not independently selected from the one in Fe, Mn, Ni, Co, V, Ti, Cu, Zn, Y, Zr, Nb, Mo, Te, Ru, Rh, Sb, Ag, Cd, La, Ta, W, Pt, Au or Cr, 0≤x≤1,0≤y≤1;
Li 1-zna zni xco ymn 1-x-yo 2in 0≤x≤1; 0≤y≤1; 0≤z≤1;
Li 2ru 1 – ymn yo 3in 0≤y≤1;
XLi 2mnO 3(1-x) LiMO 2in 0≤x≤0.5, M is Ni, Mn or Co;
LiMXO 4in M be Fe, Mn, Ni, Co, V, Ti or Cr, X is Si, P or S;
Li x0≤x≤8 in S;
M xv 2o 5in M be Ag, Ni or Cu, 0≤x≤1;
MoO 3-xand MS xo ymiddle M is Mo, Fe or W, 0≤x≤2,0≤y≤2;
Described lithium ion battery negative material is selected from least one in Li, C, Si, Sn or Ge, or the alloy of at least one in Li, C, Si, Sn or Ge, or the oxide of at least one in Li, C, Si, Sn or Ge or nitride, or described lithium ion battery negative material is M xa y, wherein M is Ti, V, Fe, Ni, Co, Mn, Cu, Cr or Zn, A is O or N, 1≤x≤3,1≤y≤5;
Described sodium-ion battery positive electrode is selected from Na xk ymO 2, Na zm xk yn 1-x-yo 2, NaMXO 4, Na xmS y, M xv 2o 5, MoO 3-x, Na xwO 3-yin at least one;
Na xy ymO 2in M be Mn, Ni or Co, Y is Li, K or Rb, x+y<1;
Na zm xk yn 1-x-yo 2in M be Fe, Mn, Ni, Co, V, Ti or Cr, 0≤x≤1,0≤y≤1, z<1;
NaMXO 4in M be Fe, Mn, Ni, Co, V, Ti or Cr, X is Si, P or S;
Na xmS yin M be Ti, Nb, Ta, Mo, Cr, V or W, 0<x<2,1≤y≤3;
M xv 2o 5in M be Ag, Ni or Cu, 0≤x≤1;
MoO 3-xand Na xwO 3-ymiddle 0<x<2,0≤y≤1;
Described anode material of lithium-ion battery is selected from least one in binary or the ternary alloy three-partalloy of Na, C or Na and Pb, Sn, Bi, Ga, Ce, Si composition;
Described anode of magnesium ion battery material is selected from Mo 6t 8, Mo 6s xse y, MgMnO 3, MgFeSiO 4, MgTi 2o 5, Cu 0.1doped VO x, S, SMn doped V 2o 5, at least one in DMcT-PAn/Mg, CMS-Pan/Mg, PDTDA/Mg;
Mo 6t 8middle T is S or Se; Mo 6s xse ymiddle x+y=8;
Described Magnesium ion battery negative material is selected from least one in Mg metal and alloy thereof;
Described aluminium ion cell positive material can be MnO 2, Mn 2o 4, AlMn 2o 4, Ti (AlCl 4) 2, MnCl (AlCl 4), Co (AlCl 4) 2, V 2o 5, at least one;
Described aluminium ion cell negative electrode material is at least one in Al or Al alloy.
8. the application in lithium ion battery, sodium-ion battery, Magnesium ion battery or aluminium ion battery according to the combination electrode described in claim 1-7 any one.
9. according to the preparation method of the combination electrode described in claim 1-7 any one, it is characterized in that: comprise the following steps,
A. carbon nano-tube and active material are uniformly dispersed;
B. finely dispersed carbon nano-tube and active material compound are prepared into the film with three-dimensional porous network configuration;
C. solid electrolyte is coated in three-dimensional porous network and on film surface, forms combination electrode.
10. preparation method according to claim 9, is characterized in that: described step b adopts vacuum filtration method or natural sediment method to be prepared into three-dimensional porous network thin-film;
Described step c adopts Vacuum Coating method, cladding process or soaks solidification method solid electrolyte is coated in three-dimensional porous network and on film surface.
CN201310726380.2A 2013-12-25 2013-12-25 Combined electrode of battery and preparation method thereof Pending CN103730630A (en)

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CN114628178B (en) * 2022-03-16 2024-03-19 桂林金格电工电子材料科技有限公司 Preparation method of consumable electrode of copper-chromium contact
CN115360344A (en) * 2022-10-21 2022-11-18 江苏智纬电子科技有限公司 Composite positive electrode material for sodium ion battery and preparation method thereof
CN115360344B (en) * 2022-10-21 2023-02-10 江苏智纬电子科技有限公司 Composite positive electrode material for sodium ion battery and preparation method thereof

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Application publication date: 20140416