CN105489880B - A kind of secondary sode cell of solid-state compound storage sodium anode and preparation method thereof - Google Patents

A kind of secondary sode cell of solid-state compound storage sodium anode and preparation method thereof Download PDF

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CN105489880B
CN105489880B CN201511027198.3A CN201511027198A CN105489880B CN 105489880 B CN105489880 B CN 105489880B CN 201511027198 A CN201511027198 A CN 201511027198A CN 105489880 B CN105489880 B CN 105489880B
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sodium
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sodium ion
anode
layer
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CN105489880A (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 present invention relates to a kind of secondary sode cell of solid-state compound storage sodium anodes and preparation method thereof, are included as the electrode active material of any one in sodium manganate, titanium phosphate sodium and the sodium ion conductor at least one of sodium perchlorate, sodium hexafluoro phosphate.Preparation process of the present invention is simple, at low cost, and the prepared secondary sode cell of room temperature-operating solid-state has good energy density, and safe.

Description

A kind of secondary sode cell of solid-state compound storage sodium anode and preparation method thereof
Technical field
The invention discloses a kind of secondary sode cells of solid-state described in compound storage sodium anode and preparation method thereof and use Prepared by compound storage sodium anode can be in the secondary sode cell of high specific energy solid-state and preparation method of room temperature-operating, and in particular to a kind of The secondary electricity of room temperature-operating solid-state sodium being made of sodium metal negative electrode, sodium ion conductivity ceramics electrolyte and solid union storage sodium anode Pond belongs to solid state battery preparation field.
Background technology
Currently, lithium ion battery is widely used in portable electronic device and extensive energy-accumulating power station, and still, lithium member Content is few in the plain expensive and earth's crust, and as it is gradually applied to electric vehicle, the demand of lithium will greatly increase, and the reserves of lithium It is limited, and is unevenly distributed, this may becomes one for developing for the long-life energy-storage battery of extensive energy storage Major issue.Sodium element and elemental lithium have similar physicochemical characteristics and storage mechanism, and since sodium is reserves in the earth's crust Six abundant elements, it is widely distributed, therefore the room temperature sodium-ion battery technology that development is directed to extensive stored energy application has weight The strategic importance wanted obtains the extensive concern of each seminar of the world again in recent years.Compared with lithium ion battery, sodium-ion battery Advantage be its energy density height, it is meant that the their quality the big more can store more energy, suitable for extensive storage Energy.
Solid-state sodium-ion battery substitutes the organic liquid electrolyte that uses in sodium-ion battery using solid electrolyte, can be with The safety of battery is greatly improved.Currently, the research of solid-state sodium-ion battery has focused largely on solid electrolyte, and take Obtained significant effect.French Lalere team is prepared for NASICON solid electrolytes being the solid-state sodium-ion battery supported [non-patent literature 1], battery use Na3V2(PO4)3Make symmetry electrode, is run at 200 DEG C, operating voltage 1.8V, cell thickness 560 microns.Tao et al. is prepared for β "-Al2O3Solid electrolyte is the solid-state sodium-ion battery [non-patent literature 2] of support, Battery can possess 152mAhg at 350 DEG C-1Capacity, thickness be 220 microns.The standby solid-state sodium ion of above-mentioned duty Although battery solves the problems, such as traditional organic electrolyte leakage, but hot operation equally brings security risk.
Bibliography：
Non-patent literature 1Lalere, F.；Leriche,J.B.；Courty,M.；Boulineau,S.；Viallet,V.； Masquelier,C.；Seznec,V.,An all-solid state NASICON sodium battery operating at 200℃.J Power Sources 2014,247,975-980.
Non-patent literature 2Wei, T.；Gong,Y.；Zhao,X.；Huang,K.,An All-Ceramic Solid-State Rechargeable Na+-Battery Operated at Intermediate Temperatures.Adv Funct Mater 2014,24(34),5380-5384.。
Invention content
The present invention proposes a kind of solid union storage sodium anode, which can make electrode have lower boundary with electrolyte The safety of battery greatly improved in face impedance.The invention also provides a kind of secondary sode cell of room temperature-operating high specific energy solid-state, Sodium ion conductivity ceramics electrolyte layer is set between sodium metal negative electrode layer and corresponding solid union storage sodium anode layer. The design can effectively inhibit the Na dendritic growths during circulating battery, improve safety and the cyclicity of battery.
The secondary sode cell of solid-state proposed by the present invention compound storage sodium anode is included as appointing in sodium manganate, titanium phosphate sodium It anticipates a kind of electrode active material and the sodium ion conductor at least one of sodium perchlorate, sodium hexafluoro phosphate.Just using this The secondary sode cell of solid-state extremely obtained can room temperature-operating, have high specific energy, battery operating voltage ranging from 0.1V-3.8V, Battery is without dendritic growth phenomenon.
The secondary sode cell of solid-state proposed by the present invention compound storage sodium anode, the positive active material and the sodium ion The mass ratio of conductor is preferably 5:1-17:1, more preferably 10:1-15:1.
Include being born by what sheet metal sodium was constituted the present invention also provides a kind of secondary sode cell of room temperature-operating high specific energy solid-state Pole layer and is set between the anode layer and negative electrode layer the compound storage sodium anode layer corresponding with the negative electrode layer Sodium ion conductivity ceramics electrolyte layer.
The preferably described sodium ion conductivity ceramics electrolyte layer is Na- β "-Al2O3、Na3Zr2Si2PO12In at least one Kind.
Also, the secondary sode cell of room temperature-operating high specific energy solid-state of the present invention, the solid union therein stores up sodium anode layer, Thickness is preferably 20-500 microns.The sodium metal negative electrode layer is preferably sheet sodium metal, and thickness is preferably 20-500 microns.Institute It is preferably 50-200 microns to state sodium ion conductivity ceramics electrolyte layer thickness.
The present invention provides a kind of preparation method of compound storage sodium anode, including：By the electrode active material and sodium ion Conductor is evenly mixed in acetone soln, is persistently stirred under 40-80 DEG C of heating condition 2-20 hours until obtaining uniform colloidal sol State liquid；The dissolved colloidal state liquid is dried, solid union storage sodium anode is made.
Preferably, in addition to electrode active material, sodium ion conductor, also while conductive additive, binder is added, with electrode Active material, sodium ion conductor are evenly mixed in acetone soln together the dissolved colloidal state liquid is made.
Preferably, being total with the additive amount of the electrode active material, sodium ion conductor, conductive additive and binder The mass fraction of amount, the then positive active material wherein added is 30%-85%, the quality point of the sodium ion conductor Number is 5%-30%, and the mass fraction of the conductive additive is 5%-30%, and the mass fraction of the binder is 5%- 10%.
Preferably, the conductive additive is at least one of acetylene black, graphite, carbon black.
Preferably, the binder is Kynoar, Kynoar-hexafluoropropene, hydroxypropyl methylcellulose, polytetrafluoro At least one of ethylene.
Meanwhile the present invention also provides a kind of preparation methods of the secondary sode cell of room temperature-operating high specific energy solid-state, by institute The side that dissolved colloidal state liquid is applied directly to the sodium ion conductivity ceramics electrolyte layer is stated, is obtained after drying close with electrolyte The solid union of contact stores up sodium anode layer, and the negative electrode layer is compressed on the another of the sodium ion conductivity ceramics electrolyte layer Side is to be made the secondary sode cell of solid-state.Its preparation process is simple, at low cost, the prepared secondary sodium of room temperature-operating solid-state Battery has good energy density, and safe.
Description of the drawings
Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium anode and solid electrolyte interface scanning electron microscope (SEM) photograph；
Fig. 2 is appearance of the secondary sode cell of room temperature-operating solid-state of the preparation of the embodiment of the present invention 2 in 100 charge and discharge cycles Amount-cyclic curve；
Fig. 3 is the capacitance-voltage curves of the secondary sode cell of room temperature-operating solid-state prepared by the embodiment of the present invention 3.
Specific implementation mode
The compound storage sodium anode of the secondary sode cell of solid-state proposed by the present invention is suitable for sodium ion conductivity ceramics electrolyte, packet Containing electrode active material and sodium ion conductor.Electrode active material can be any one in sodium manganate, titanium phosphate sodium.Sodium from Sub- conductor can be at least one of sodium perchlorate, sodium hexafluoro phosphate.In above-mentioned electrode active material, the sodium manganate material Chemical formula be NaxMnO2, the value of x is as follows：X is 0.44 or x is 1.The chemical formula of the titanium phosphate sodium is NaTi2(PO4)3。 In addition, the mass ratio of the positive active material and the sodium ion conductor can be 5:1-17:1.The amount of positive active material Can amount suitable with the amount of sodium ion conductor or more than sodium ion conductor, but if 2 mass ratio is more than 17, conductivity It can significantly reduce, or when the quality of positive active material is fewer than the amount of sodium ion conductor, sodium ion just can not be participated in normally Reaction.
The secondary sode cell of the solid-state of the present invention preparation of compound storage sodium anode, is made by following methods：By the electricity Pole active material is evenly mixed in sodium ion conductor in acetone soln, and it is small that 2-20 is persistently stirred under 40-80 DEG C of heating condition Shi Zhizhi obtains uniform dissolved colloidal state liquid；The dissolved colloidal state liquid is dried, solid union storage sodium anode is made.More as one Specific example, when preparing the dissolved colloidal state liquid, by the positive active material, sodium ion conductor, conductive additive and Binder is added in acetone soln simultaneously, is allowed to uniformly mix, and is stirred continuously until to obtain uniform dissolved colloidal state liquid under heating condition The dissolved colloidal state liquid is dried and solid union storage sodium anode is made by body.The positive active material, sodium ion conductor, conduction The mass ratio of additive, binder and acetone is (6-17):(1-6):(1-6):(1-2):200.The conductive additive is second At least one of acetylene black, graphite, carbon black.The binder is Kynoar, Kynoar-hexafluoropropene, hydroxypropyl first At least one of cellulose, polytetrafluoroethylene (PTFE).
Using compound storage sodium anode proposed by the present invention as the anode layer of battery, sheet metal sodium as negative electrode layer, in institute Setting sodium ion conductivity ceramics electrolyte layer between anode layer and negative electrode layer is stated, then can be prepared into the secondary sode cell of solid-state.This hair The secondary sode cell of room temperature solid of bright proposition can effectively inhibit the Na dendritic growths during circulating battery, improve the peace of battery Full property and cyclicity.The design of solid union storage sodium anode makes electrode have lower interface impedance with electrolyte.The sodium from Subconductivity ceramic electrolyte layer can be Na- β "-Al2O3、Na3Zr2Si2PO12At least one of.The solid-state therein is multiple Storage sodium anode layer is closed, thickness is preferably 20-500 microns.The sodium metal negative electrode layer is preferably sheet sodium metal, and thickness is preferably 20-500 microns, more preferably 20-100 microns.The sodium ion conductivity ceramics electrolyte layer thickness is preferably 50-200 microns.
Aforementioned dissolved colloidal state liquid is coated uniformly on sodium ion conductivity ceramics electrolyte by silk-screen printing or other methods The side of layer obtains storing up sodium anode layer with the solid union that electrolyte is in close contact after drying.The sodium ion conductivity ceramics electricity Solution matter layer is Na- β "-Al2O3、Na3Zr2Si2PO12At least one of, electrolyte thickness is 50-200 microns, solid union storage The thickness of sodium anode layer is 20-500 microns.Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium anode and solid state electrolysis Matter interface scanning electron microscope, from figure 1 it appears that electrode is in close contact with electrolyte.Through electricity known to AC impedance spectrometry There is lower interface impedance between pole and sodium ion conductivity ceramics electrolyte layer, and use sodium ion conductivity ceramics electrolyte It solves the problems, such as traditional electrolyte leakage, the safety of battery greatly improved.
Sodium metal negative electrode is compressed on to the other side of sodium ion conductivity ceramics electrolyte layer, the three-layered node being in close contact Solid state battery is encapsulated in metal button cell or similar device to get to the secondary sodium of room temperature-operating high specific energy solid-state by structure Battery.The sodium metal negative electrode is sheet sodium metal negative electrode, and thickness can be 20-500 microns.
Fig. 2 is appearance of the secondary sode cell of room temperature-operating solid-state of the preparation of the embodiment of the present invention 2 in 100 charge and discharge cycles Amount-cyclic curve.It can be seen that battery after activation stablize by performance.The secondary sode cell energy of room temperature solid proposed by the present invention Enough Na dendritic growths effectively inhibited during circulating battery, improve safety and the cyclicity of battery.Fig. 3 is that the present invention is implemented The capacitance-voltage curves of the secondary sode cell of room temperature-operating solid-state prepared by example 3.Battery has steady at 2.05V as we know from the figure Fixed discharge platform.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
By 0.3gNaMnO2、0.3g NaPF6Solution, 0.3g acetylene blacks, that 0.1gPVDF-HFP is evenly mixed in 10g acetone is molten In liquid, 4h is persistently stirred at 50 DEG C, obtains uniform dissolved colloidal state liquid；
Uniform dissolved colloidal state liquid in (1) is coated uniformly on β "-Al by the method for silk-screen printing2O3Bath surface, electricity 170 microns of matter thickness is solved, obtains storing up sodium anode layer with the solid union that electrolyte is in close contact after drying, thickness is 60 microns；
Metallic sodium piece is compressed on to the other side of sodium ion conductivity ceramics electrolyte layer, thickness is 70 microns.By solid-state electricity Pond is encapsulated in button cell to get to the secondary sode cell of room temperature-operating high specific energy solid-state；
Fig. 1 is that solid union prepared by the embodiment of the present invention 1 stores up sodium anode and solid electrolyte interface scanning electron microscope (SEM) photograph, from As can be seen that electrode is in close contact with electrolyte in Fig. 1.Through electrode known to AC impedance spectrometry and sodium ion conductivity ceramics electricity There is lower interface impedance between solution matter layer.
Embodiment 2
By 0.3gNaTi2(PO4)3、0.3g NaClO4Solution, 0.3g acetylene blacks, 0.1gPVDF-HFP are evenly mixed in 10g In acetone soln, 4h is persistently stirred at 50 DEG C, obtains uniform dissolved colloidal state liquid；
Uniform dissolved colloidal state liquid in (1) is coated uniformly on β "-Al by the method for silk-screen printing2O3Bath surface dries It obtains storing up sodium anode layer with the solid union that electrolyte is in close contact after dry, thickness is 52 microns；
Metallic sodium piece is compressed on to the other side of sodium ion conductivity ceramics electrolyte layer, thickness is 70 microns.By solid-state electricity Pond is encapsulated in button cell to get to the secondary sode cell of room temperature-operating high specific energy solid-state；
Fig. 2 is appearance of the secondary sode cell of room temperature-operating solid-state of the preparation of the embodiment of the present invention 2 in 100 charge and discharge cycles Amount-cyclic curve.Battery after activation stablize by performance as we know from the figure.
Embodiment 3
By 0.85gNaTi2(PO4)3、0.05g NaClO4Solution, 0.05g acetylene blacks, 0.05gPVDF are evenly mixed in 10g In acetone soln, 12h is persistently stirred at 50 DEG C, obtains uniform dissolved colloidal state liquid；
Uniform dissolved colloidal state liquid in (1) is coated uniformly on β "-Al by the method for silk-screen printing2O3Bath surface dries It obtains storing up sodium anode layer with the solid union that electrolyte is in close contact after dry, thickness is 83 microns；
Metallic sodium piece is compressed on to the other side of sodium ion conductivity ceramics electrolyte layer, thickness is 70 microns.By solid-state electricity Pond is encapsulated in button cell to get to the secondary sode cell of room temperature-operating high specific energy solid-state.
Embodiment 4
By 0.3gNaTi2(PO4)3、0.3g NaClO4Solution, 0.3g carbon blacks, 0.1gPVDF-HFP are evenly mixed in 10g third In ketone solution, 12h is persistently stirred at 50 DEG C, obtains uniform dissolved colloidal state liquid；
Uniform dissolved colloidal state liquid in (1) is coated uniformly on Na by the method for silk-screen printing3Zr2Si2PO12Electrolyte meter Face obtains storing up sodium anode layer with the solid union that electrolyte is in close contact after drying, and thickness is 100 microns；
Metallic sodium piece is compressed on to the other side of sodium ion conductivity ceramics electrolyte layer, thickness is 70 microns.By solid-state electricity Pond is encapsulated in button cell to get to the secondary sode cell of room temperature-operating high specific energy solid-state.

Claims (10)

1. a kind of secondary sode cell of solid-state stores up sodium anode with solid union, which is characterized in that be included as in sodium manganate, titanium phosphate sodium The electrode active material of any one and sodium ion conductor at least one of sodium perchlorate, sodium hexafluoro phosphate, it is described The mass ratio of electrode active material and the sodium ion conductor is 5:1-17:1.
2. a kind of secondary sode cell of solid-state prepared using anode described in claim 1, which is characterized in that including by lamellar gold Belong to anode layer, the Yi Jishe that negative electrode layer, the solid union storage sodium anode corresponding with the negative electrode layer that sodium is constituted are constituted The sodium ion conductivity ceramics electrolyte layer being placed between the anode layer and negative electrode layer.
3. battery according to claim 2, which is characterized in that the sodium ion conductivity ceramics electrolyte layer is Na- β ' '- Al2O3、Na3Zr2Si2PO12At least one of.
4. the preparation method of solid union storage sodium anode described in a kind of claim 1, it is characterised in that including：
The electrode active material and sodium ion conductor are evenly mixed in acetone soln, held under 40-80 DEG C of heating condition It is continuous to stir 2-20 hours until obtaining uniform dissolved colloidal state liquid；
The dissolved colloidal state liquid is dried, solid union storage sodium anode is made.
5. according to the method described in claim 4, it is characterized in that, going back while conductive additive, binder and electrode active being added Property substance, sodium ion conductor uniformly mixing be made the dissolved colloidal state liquid.
6. according to the method described in claim 5, it is characterized in that, adding in the electrode active material, sodium ion conductor, conduction In the total amount for adding agent and binder, the mass fraction of the electrode active material is 30%-85%, the quality of the sodium ion conductor Score is 5%-30%, and the mass fraction of the conductive additive is 5%-30%, and the mass fraction of the binder is 5%-10%.
7. method according to claim 5 or 6, which is characterized in that the conductive additive is graphite, in carbon black at least It is a kind of.
8. the method according to the description of claim 7 is characterized in that the conductive additive is acetylene black.
9. method according to claim 5 or 6, which is characterized in that the binder is Kynoar, polyvinylidene fluoride At least one of alkene-hexafluoropropene, hydroxypropyl methylcellulose, polytetrafluoroethylene (PTFE).
10. a kind of preparation method of battery as claimed in claim 2 or claim 3, which is characterized in that including：
The electrode active material is uniformly mixed with sodium ion conductor, persistently stirred under 40-80 DEG C of heating condition 2 hours- 20 hours until obtain uniform dissolved colloidal state liquid；The dissolved colloidal state liquid is coated uniformly on the sodium ion conductivity ceramics electrolysis The side of matter layer obtains the anode layer being in close contact with electrolyte after drying；
The negative electrode layer is compressed on the other side of the sodium ion conductivity ceramics electrolyte layer so that the secondary sodium of solid-state is made Battery.
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"Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds";Yoshinori Noguchi et al.;《Electrichimica Acta》;20121121;第101卷;摘要、实验部分、结果与讨论部分 *

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