CN105489880A - Composite sodium-storage positive electrode for solid-state secondary sodium battery and preparation method for composite sodium-storage positive electrode - Google Patents

Composite sodium-storage positive electrode for solid-state secondary sodium battery and preparation method for composite sodium-storage positive electrode Download PDF

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CN105489880A
CN105489880A CN201511027198.3A CN201511027198A CN105489880A CN 105489880 A CN105489880 A CN 105489880A CN 201511027198 A CN201511027198 A CN 201511027198A CN 105489880 A CN105489880 A CN 105489880A
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sodium
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sodium ion
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battery
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CN105489880B (en
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刘宇
赵宽
夏骥
贺诗阳
张书明
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Shanghai Institute of Ceramics of CAS
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a composite sodium-storage positive electrode for a solid-state secondary sodium battery and a preparation method for the composite sodium-storage positive electrode. The composite sodium-storage positive electrode comprises an electrode active substance selected from any one kind of sodium manganate and sodium-titanium phosphate, and a sodium ion conductor selected from any one kind of sodium perchlorate and sodium hexafiuorophosphate. The preparation method is simple in preparation process and low in cost; and the prepared solid-state secondary sodium battery operating at the room temperature is high in energy density and high in safety.

Description

A kind of solid-state secondary sode cell compound storage sodium positive pole and preparation method thereof
Technical field
The invention discloses a kind of solid-state secondary sode cell compound storage sodium positive pole and preparation method thereof, and use described compound to store up prepared by sodium positive pole can in the solid-state secondary sode cell of the high specific energy of room temperature-operating and preparation method, be specifically related to a kind of solid-state sodium rechargeable battery of room temperature-operating be made up of sodium metal negative electrode, sodium ion conductivity ceramics electrolyte and solid union storage sodium positive pole, belong to solid state battery preparation field.
Background technology
At present, lithium ion battery is widely used in portable electric appts and extensive energy-accumulating power station, but, elemental lithium expensive and in the earth's crust content few, along with it is applied to electric automobile gradually, the demand of lithium will increase greatly, and the reserves of lithium are limited, and skewness, this, for the long-life energy-storage battery of the extensive energy storage of development, may become a major issue.Sodium element and elemental lithium have similar physicochemical characteristics and storage mechanism, and due to sodium be the element that in the earth's crust, reserves the 6th are abundant, widely distributed, therefore develop the room temperature sodium-ion battery technology being directed to extensive stored energy application and there is important strategic importance, again obtain the extensive concern of each seminar of the world in recent years.Compared with lithium ion battery, the advantage of sodium-ion battery is that its energy density is high, means that their quality more can store more multi-energy more greatly, is suitable for extensive energy storage.
Solid-state sodium-ion battery uses solid electrolyte to substitute the organic liquid electrolyte used in sodium-ion battery, greatly can improve the fail safe of battery.At present, the research of solid-state sodium-ion battery concentrates on solid electrolyte mostly, and has achieved significant effect.Lalere team of France has prepared with the solid-state sodium-ion battery [non-patent literature 1] of NASICON solid electrolyte for supporting, and battery adopts Na 3v 2(PO 4) 3make symmetry electrode, run at 200 DEG C, operating voltage 1.8V, cell thickness 560 microns.The people such as Tao have prepared with β "-Al 2o 3solid electrolyte is the solid-state sodium-ion battery [non-patent literature 2] supported, and battery can have 152mAhg at 350 DEG C -1capacity, thickness is 220 microns.Although the standby solid-state sodium-ion battery of above-mentioned duty solves traditional organic electrolyte leakage problem, hot operation brings potential safety hazard equally.
List of references:
Non-patent literature 1Lalere, F.; Leriche, J.B.; Courty, M.; Boulineau, S.; Viallet, V.; Masquelier, C.; Seznec, V., Anall-solidstateNASICONsodiumbatteryoperatingat200 DEG C of .JPowerSources2014,247,975-980.
Non-patent literature 2Wei, T.; Gong, Y.; Zhao, X.; Huang, K., AnAll-CeramicSolid-StateRechargeableNa+-BatteryOperateda tIntermediateTemperatures.AdvFunctMater2014,24 (34), 5380-5384..
Summary of the invention
The present invention proposes a kind of solid union storage sodium positive pole, this positive pole can make electrode and electrolyte have lower interface impedance, significantly improves the fail safe of battery.The invention allows for the solid-state secondary sode cell of a kind of room temperature-operating high specific energy, sodium ion conductivity ceramics dielectric substrate is set between sodium metal negative electrode layer and the solid union storage sodium anode layer corresponded.This design effectively can suppress the Na dendritic growth in circulating battery process, improves fail safe and the cyclicity of battery.
The solid-state secondary sode cell compound storage sodium positive pole that the present invention proposes, is included as any one the electrode active material in sodium manganate, titanium phosphate sodium and the sodium ion conductor at least one in sodium perchlorate, sodium hexafluoro phosphate.The solid-state secondary sode cell using this positive pole obtained can at room temperature-operating, there is high specific energy, battery operating voltage scope is 0.1V-3.8V, and battery is without dendritic growth phenomenon.
The solid-state secondary sode cell compound storage sodium positive pole that the present invention proposes, the mass ratio of described positive active material and described sodium ion conductor is preferably 5:1-17:1, is more preferably 10:1-15:1.
The present invention also provides a kind of room temperature-operating high specific energy solid-state secondary sode cell, and the described compound comprising the negative electrode layer that is made up of sheet metal sodium corresponding with described negative electrode layer is stored up sodium anode layer and is arranged at the sodium ion conductivity ceramics dielectric substrate between described anode layer and negative electrode layer.
Preferably described sodium ion conductivity ceramics dielectric substrate is Na-β "-Al 2o 3, Na 3zr 2si 2pO 12in at least one.
Again, the solid-state secondary sode cell of room temperature-operating high specific energy of the present invention, described solid union storage sodium anode layer wherein, thickness is preferably 20-500 micron.Described sodium metal negative electrode layer is preferably sheet sodium metal, and thickness is preferably 20-500 micron.Described sodium ion conductivity ceramics dielectric substrate thickness is preferably 50-200 micron.
The invention provides the preparation method of a kind of compound storage sodium positive pole, comprising: described electrode active material and sodium ion conductor are evenly mixed in acetone soln, under 40-80 DEG C of heating condition Keep agitation 2-20 hour until obtain even dissolved colloidal state liquid; Described dissolved colloidal state liquid is dried obtained solid union storage sodium positive pole.
Preferably, except electrode active material, sodium ion conductor, also add conductive additive, binding agent simultaneously, be evenly mixed in together with electrode active material, sodium ion conductor in acetone soln with obtained described dissolved colloidal state liquid.
Preferably, with the addition of described electrode active material, sodium ion conductor, conductive additive and binding agent for total amount, the mass fraction of then wherein added described positive active material is 30%-85%, the mass fraction of described sodium ion conductor is 5%-30%, the mass fraction of described conductive additive is 5%-30%, and the mass fraction of described binding agent is 5%-10%.
Preferably, described conductive additive is at least one in acetylene black, graphite, carbon black.
Preferably, described binding agent is at least one in Kynoar, Kynoar-hexafluoropropylene, Hydroxypropyl methylcellulose, polytetrafluoroethylene.
Simultaneously, present invention also offers the preparation method of the solid-state secondary sode cell of a kind of room temperature-operating high specific energy, described dissolved colloidal state liquid is directly coated in the side of described sodium ion conductivity ceramics dielectric substrate by it, obtain after oven dry storing up sodium anode layer with the described solid union of electrolyte close contact, described negative electrode layer is compressed on the opposite side of described sodium ion conductivity ceramics dielectric substrate with obtained described solid-state secondary sode cell.Its preparation technology is simple, and cost is low, and prepared room temperature-operating solid-state secondary sode cell has good energy density, and fail safe is high.
Accompanying drawing explanation
Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium positive pole and solid electrolyte interface scanning electron microscope (SEM) photograph;
Fig. 2 is the capacity versus cycle curve of the solid-state secondary sode cell of room temperature-operating in 100 charge and discharge cycles prepared by the embodiment of the present invention 2;
Fig. 3 is the capacitance-voltage curves of the solid-state secondary sode cell of room temperature-operating prepared by the embodiment of the present invention 3.
Embodiment
The solid-state secondary sode cell compound storage sodium positive pole that the present invention proposes is applicable to sodium ion conductivity ceramics electrolyte, comprises electrode active material and sodium ion conductor.Electrode active material can be any one in sodium manganate, titanium phosphate sodium.Sodium ion conductor can be at least one in sodium perchlorate, sodium hexafluoro phosphate.In above-mentioned electrode active material, the chemical formula of described sodium manganate material is Na xmnO 2, the value of x is as follows: x be 0.44 or x be 1.The chemical formula of described titanium phosphate sodium is NaTi 2(PO 4) 3.In addition, the mass ratio of described positive active material and described sodium ion conductor can be 5:1-17:1.The amount of positive active material can with the amount of sodium ion conductor quite or be greater than the amount of sodium ion conductor, if but the mass ratio of 2 more than 17 time, conductance can significantly reduce, or when the quality of positive active material is fewer than the amount of sodium ion conductor, sodium ion just normally cannot participate in reaction.
The preparation of the present invention's solid-state secondary sode cell compound storage sodium positive pole, be by following method obtain: described electrode active material and sodium ion conductor are evenly mixed in acetone soln, under 40-80 DEG C of heating condition Keep agitation 2-20 hour until obtain even dissolved colloidal state liquid; Described dissolved colloidal state liquid is dried obtained solid union storage sodium positive pole.As an example more specifically, when preparing described dissolved colloidal state liquid, described positive active material, sodium ion conductor, conductive additive and binding agent are added in acetone soln simultaneously, make it Homogeneous phase mixing, described dissolved colloidal state liquid, until obtain even dissolved colloidal state liquid, is dried obtained solid union storage sodium positive pole by Keep agitation under heating condition.The mass ratio of described positive active material, sodium ion conductor, conductive additive, binding agent and acetone is (6-17): (1-6): (1-6): (1-2): 200.Described conductive additive is at least one in acetylene black, graphite, carbon black.Described binding agent is at least one in Kynoar, Kynoar-hexafluoropropylene, Hydroxypropyl methylcellulose, polytetrafluoroethylene.
The compound storage sodium positive pole that the present invention is proposed as the anode layer of battery, sheet metal sodium as negative electrode layer, sodium ion conductivity ceramics dielectric substrate is set between described anode layer and negative electrode layer, then can be prepared into solid-state secondary sode cell.The room temperature solid secondary sode cell that the present invention proposes effectively can suppress the Na dendritic growth in circulating battery process, improves fail safe and the cyclicity of battery.The design of solid union storage sodium positive pole makes electrode and electrolyte have lower interface impedance.Described sodium ion conductivity ceramics dielectric substrate can be Na-β "-Al 2o 3, Na 3zr 2si 2pO 12in at least one.Described solid union storage sodium anode layer wherein, thickness is preferably 20-500 micron.Described sodium metal negative electrode layer is preferably sheet sodium metal, and thickness is preferably 20-500 micron, is more preferably 20-100 micron.Described sodium ion conductivity ceramics dielectric substrate thickness is preferably 50-200 micron.
Aforementioned dissolved colloidal state liquid is evenly coated in the side of sodium ion conductivity ceramics dielectric substrate by silk screen printing or other method, obtains after oven dry storing up sodium anode layer with the solid union of electrolyte close contact.Described sodium ion conductivity ceramics dielectric substrate is Na-β "-Al 2o 3, Na 3zr 2si 2pO 12in at least one, electrolyte thickness is 50-200 micron, and the thickness of solid union storage sodium anode layer is 20-500 micron.Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium positive pole and solid electrolyte interface scanning electron microscope (SEM) photograph, as can be seen from Figure 1, and electrode and electrolyte close contact.Through having lower interface impedance between the known electrode of AC impedance spectrometry and sodium ion conductivity ceramics dielectric substrate, and adopting sodium ion conductivity ceramics electrolyte to solve traditional electrolyte leakage problem, significantly improve the fail safe of battery.
Sodium metal negative electrode is compressed on the opposite side of sodium ion conductivity ceramics dielectric substrate, obtains the three-decker of close contact, solid state battery is encapsulated in metal button cell or similar device, namely obtain the solid-state secondary sode cell of room temperature-operating high specific energy.Described sodium metal negative electrode is sheet sodium metal negative electrode, and thickness can be 20-500 micron.
Fig. 2 is the capacity versus cycle curve of the solid-state secondary sode cell of room temperature-operating in 100 charge and discharge cycles prepared by the embodiment of the present invention 2.As we know from the figure, battery stable performance after activation.The room temperature solid secondary sode cell that the present invention proposes effectively can suppress the Na dendritic growth in circulating battery process, improves fail safe and the cyclicity of battery.Fig. 3 is the capacitance-voltage curves of the solid-state secondary sode cell of room temperature-operating prepared by the embodiment of the present invention 3.Battery has stable discharge platform at 2.05V place as we know from the figure.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
By 0.3gNaMnO 2, 0.3gNaPF 6solution, 0.3g acetylene black, 0.1gPVDF-HFP are evenly mixed in 10g acetone soln, Keep agitation 4h at 50 DEG C, obtain even dissolved colloidal state liquid;
Dissolved colloidal state liquid even in (1) is evenly coated in β by the method for silk screen printing "-Al 2o 3bath surface, electrolyte thickness 170 microns, obtain after oven dry storing up sodium anode layer with the solid union of electrolyte close contact, thickness is 60 microns;
Sodium metal sheet is compressed on the opposite side of sodium ion conductivity ceramics dielectric substrate, thickness is 70 microns.Solid state battery is encapsulated in button cell, namely obtains the solid-state secondary sode cell of room temperature-operating high specific energy;
Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium positive pole and solid electrolyte interface scanning electron microscope (SEM) photograph, as can be seen from Figure 1, and electrode and electrolyte close contact.Through there is lower interface impedance between the known electrode of AC impedance spectrometry and sodium ion conductivity ceramics dielectric substrate.
Embodiment 2
By 0.3gNaTi 2(PO 4) 3, 0.3gNaClO 4solution, 0.3g acetylene black, 0.1gPVDF-HFP are evenly mixed in 10g acetone soln, Keep agitation 4h at 50 DEG C, obtain even dissolved colloidal state liquid;
Dissolved colloidal state liquid even in (1) is evenly coated in β by the method for silk screen printing "-Al 2o 3bath surface, obtain after oven dry storing up sodium anode layer with the solid union of electrolyte close contact, thickness is 52 microns;
Sodium metal sheet is compressed on the opposite side of sodium ion conductivity ceramics dielectric substrate, thickness is 70 microns.Solid state battery is encapsulated in button cell, namely obtains the solid-state secondary sode cell of room temperature-operating high specific energy;
Fig. 2 is the capacity versus cycle curve of the solid-state secondary sode cell of room temperature-operating in 100 charge and discharge cycles prepared by the embodiment of the present invention 2.Battery stable performance after activation as we know from the figure.
Embodiment 3
By 0.85gNaTi 2(PO 4) 3, 0.05gNaClO 4solution, 0.05g acetylene black, 0.05gPVDF are evenly mixed in 10g acetone soln, Keep agitation 12h at 50 DEG C, obtain even dissolved colloidal state liquid;
Dissolved colloidal state liquid even in (1) is evenly coated in β by the method for silk screen printing "-Al 2o 3bath surface, obtain after oven dry storing up sodium anode layer with the solid union of electrolyte close contact, thickness is 83 microns;
Sodium metal sheet is compressed on the opposite side of sodium ion conductivity ceramics dielectric substrate, thickness is 70 microns.Solid state battery is encapsulated in button cell, namely obtains the solid-state secondary sode cell of room temperature-operating high specific energy.
Embodiment 4
By 0.3gNaTi 2(PO 4) 3, 0.3gNaClO 4solution, 0.3g carbon black, 0.1gPVDF-HFP are evenly mixed in 10g acetone soln, Keep agitation 12h at 50 DEG C, obtain even dissolved colloidal state liquid;
Dissolved colloidal state liquid even in (1) is evenly coated in Na by the method for silk screen printing 3zr 2si 2pO 12bath surface, obtain after oven dry storing up sodium anode layer with the solid union of electrolyte close contact, thickness is 100 microns;
Sodium metal sheet is compressed on the opposite side of sodium ion conductivity ceramics dielectric substrate, thickness is 70 microns.Solid state battery is encapsulated in button cell, namely obtains the solid-state secondary sode cell of room temperature-operating high specific energy.

Claims (10)

1. a solid-state secondary sode cell compound storage sodium positive pole, is characterized in that, be included as any one the electrode active material in sodium manganate, titanium phosphate sodium and the sodium ion conductor at least one in sodium perchlorate, sodium hexafluoro phosphate.
2. solid-state secondary sode cell compound storage sodium positive pole according to claim 1, it is characterized in that, the mass ratio of described positive active material and described sodium ion conductor is 5:1-17:1.
3. the solid-state secondary sode cell using the positive pole described in claim 1 or 2 to prepare, it is characterized in that, the described compound comprising the negative electrode layer that is made up of sheet metal sodium corresponding with described negative electrode layer is stored up sodium anode layer and is arranged at the sodium ion conductivity ceramics dielectric substrate between described anode layer and negative electrode layer.
4. battery according to claim 3, is characterized in that, described sodium ion conductivity ceramics dielectric substrate is Na-β ' '-Al 2o 3, Na 3zr 2si 2pO 12in at least one.
5. a preparation method for solid union storage sodium positive pole described in claim 1 or 2, is characterized in that comprising:
Described electrode active material and sodium ion conductor are evenly mixed in acetone soln, under 40-80 DEG C of heating condition Keep agitation 2-20 hour until obtain even dissolved colloidal state liquid;
Described dissolved colloidal state liquid is dried obtained solid union storage sodium positive pole.
6. method according to claim 5, is characterized in that, also adds conductive additive, binding agent and electrode active material, sodium ion conductor Homogeneous phase mixing with obtained described dissolved colloidal state liquid simultaneously.
7. method according to claim 6, it is characterized in that, in the total amount of described electrode active material, sodium ion conductor, conductive additive and binding agent, the mass fraction of described positive active material is 30%-85%, the mass fraction of described sodium ion conductor is 5%-30%, the mass fraction of described conductive additive is 5%-30%, and the mass fraction of described binding agent is 5%-10%.
8. the method according to claim 6 or 7, is characterized in that, described conductive additive is at least one in acetylene black, graphite, carbon black.
9. the method according to any one of claim 6-8, is characterized in that, described binding agent is at least one in Kynoar, Kynoar-hexafluoropropylene, Hydroxypropyl methylcellulose, polytetrafluoroethylene.
10. a preparation method for the battery as described in claim 3 or 4, is characterized in that, comprising:
By described electrode active material and sodium ion conductor Homogeneous phase mixing, Keep agitation 2 hours-20 hours under 40-80 DEG C of heating condition is until obtain even dissolved colloidal state liquid; Described dissolved colloidal state uniform liquid is coated in the side of described sodium ion conductivity ceramics dielectric substrate, obtains after oven dry storing up sodium anode layer with the described solid union of electrolyte close contact;
Described negative electrode layer is compressed on the opposite side of described sodium ion conductivity ceramics dielectric substrate with obtained described solid-state secondary sode cell.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107799854A (en) * 2016-09-05 2018-03-13 中国科学院宁波材料技术与工程研究所 A kind of high-temperature solid sodium ion air oxygen compound energy-storage battery
CN108598394A (en) * 2018-03-30 2018-09-28 武汉理工大学 Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application
CN110165218A (en) * 2019-04-04 2019-08-23 中南大学 A kind of positive application for mending sodium agent in sodium-ion battery
CN110783621A (en) * 2019-10-18 2020-02-11 扬州扬达新能源有限公司 Water system sodium ion battery and preparation method thereof
CN115377407A (en) * 2022-01-21 2022-11-22 昆明理工大学 Treatment process for positive electrode material of all-solid-state sodium ion battery
CN115924977A (en) * 2022-12-31 2023-04-07 天津理工大学 Modified P2 type layered Mn-based oxide, preparation method thereof and application thereof as positive electrode material in sodium-ion battery
WO2024090324A1 (en) * 2022-10-28 2024-05-02 ダイキン工業株式会社 Binder for positive electrodes, electrode mixture, electrode and secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319904A (en) * 2000-03-24 2001-10-31 松下电器产业株式会社 Method for making electrode board used in cell
CN104681884A (en) * 2013-11-28 2015-06-03 Sk新技术株式会社 Sodium secondary battery
US20150180024A1 (en) * 2012-06-12 2015-06-25 Toyota Jidosha Kabushiki Kaisha Positive electrode material for sodium batteries and method for producing same
CN105098140A (en) * 2014-08-06 2015-11-25 中国科学院物理研究所 Liquid metal anode material, room-temperature liquid metal battery, and preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319904A (en) * 2000-03-24 2001-10-31 松下电器产业株式会社 Method for making electrode board used in cell
US20150180024A1 (en) * 2012-06-12 2015-06-25 Toyota Jidosha Kabushiki Kaisha Positive electrode material for sodium batteries and method for producing same
CN104681884A (en) * 2013-11-28 2015-06-03 Sk新技术株式会社 Sodium secondary battery
CN105098140A (en) * 2014-08-06 2015-11-25 中国科学院物理研究所 Liquid metal anode material, room-temperature liquid metal battery, and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YOSHINORI NOGUCHI ET AL.: ""Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds"", 《ELECTRICHIMICA ACTA》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107799854A (en) * 2016-09-05 2018-03-13 中国科学院宁波材料技术与工程研究所 A kind of high-temperature solid sodium ion air oxygen compound energy-storage battery
CN108598394A (en) * 2018-03-30 2018-09-28 武汉理工大学 Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application
CN108598394B (en) * 2018-03-30 2021-01-19 武汉理工大学 Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN110165218A (en) * 2019-04-04 2019-08-23 中南大学 A kind of positive application for mending sodium agent in sodium-ion battery
CN110165218B (en) * 2019-04-04 2021-02-19 中南大学 Application of positive electrode sodium supplement agent in sodium ion battery
CN110783621A (en) * 2019-10-18 2020-02-11 扬州扬达新能源有限公司 Water system sodium ion battery and preparation method thereof
CN115377407A (en) * 2022-01-21 2022-11-22 昆明理工大学 Treatment process for positive electrode material of all-solid-state sodium ion battery
WO2024090324A1 (en) * 2022-10-28 2024-05-02 ダイキン工業株式会社 Binder for positive electrodes, electrode mixture, electrode and secondary battery
CN115924977A (en) * 2022-12-31 2023-04-07 天津理工大学 Modified P2 type layered Mn-based oxide, preparation method thereof and application thereof as positive electrode material in sodium-ion battery

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