CN109088068A - sodium ion battery - Google Patents
sodium ion battery Download PDFInfo
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- CN109088068A CN109088068A CN201710442457.1A CN201710442457A CN109088068A CN 109088068 A CN109088068 A CN 109088068A CN 201710442457 A CN201710442457 A CN 201710442457A CN 109088068 A CN109088068 A CN 109088068A
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- ion battery
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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
- 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
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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
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a sodium ion battery, which comprises an anode sheet, a cathode sheet, a separation film and electrolyte, wherein the separation film is arranged between the cathode sheet and the anode sheet, and the electrolyte comprises a non-aqueous organic solvent and sodium salt dissolved in the non-aqueous organic solvent. The electrolyte also includes an additive dissolved in the non-aqueous organic solvent, the additive having a charge/radius ratio of cations less than that of sodium ions. The cathode active material in the cathode sheet includes a prussian blue-based material. The charge/radius ratio of the cation of the electrolyte additive is smaller than that of the sodium ion, the cation can be preferentially embedded into and separated from the Prussian blue material in the charging and discharging processes of the sodium ion battery, and the structure of the Prussian blue material is less damaged in the embedding and separating processes, so that the three-dimensional framework structure of the Prussian blue material can be stabilized, and the sodium ion battery has good cycle performance.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of sodium-ion batteries.
Background technique
It is gradually applied in electric car and energy storage field along with lithium ion battery, the supply and demand problem day of metal lithium resource
Benefit highlights.And sodium resource reserve is abundant, widely distributed, low in cost, therefore sodium-ion battery is concerned in recent years.In order to obtain
The sodium-ion battery of high-energy-density, long circulation life is obtained, scientific and technical personnel are committed to exploitation specific capacity height, sodium ion at low cost
Cell cathode active material.Compared to other types of active material of cathode, prussian blue material has specific capacity height, voltage
Platform is high, the advantages such as at low cost, is a kind of ideal chose of sodium-ion battery active material of cathode.
The structural formula of prussian blue (Prussian Blue Analogue, PBA) material is generally represented byWherein A is alkali or alkaline earth metal cation, M, M '
For transition-metal cation, it can be selected from one or more of Mn, Fe, Co, Ni, Cu, Zn etc.,For M ' (CN)6Hole, b-
H2O is water of coordination, i-H2O is interstitial water, 0 < x≤2,0 < c≤1,0 < y < 1,0≤z≤16.In PBA crystal structure, in cyano
Carbon ligand and transition-metal cation M ' complexing at hexa-coordinate octahedral structure M ' (CN)6, M ' (CN)6In octahedron not
The octahedral structure M (NC) of hexa-coordinate is also complexed into the nitrogen ligand and transition-metal cation M of coordination6, therefore M ' (CN)6Octahedral
Body and M (NC)6Octahedron, which alternates, to be connected and forms three dimensional skeletal structure.Not due to alkali or alkaline earth metal cation A
It is complexed with cyano, so alkali or alkaline earth metal cation A is present in the duct in PBA three dimensional skeletal structure, plays flat
The effect of weighing apparatus charge.
When sodium-ion battery carries out charge and discharge, alkali or alkaline earth metal cation takes off from PBA three dimensional skeletal structure
Out, it is embedded in, in the process, the three dimensional skeletal structure of PBA must keep stable, and sodium-ion battery just has the stable circulation longevity
Life.But alkali or alkaline earth metal cation inevitably causes the small of PBA lattice constant during insertion, abjection
Variation, especially when appraising at the current rate simultaneously in PBA there are two transition metal, lattice constant variation is bigger.In addition, working as PBA structure hollow
When cave is more, with the moisture in hole strong phase can occur for alkali or alkaline earth metal cation during insertion, abjection
Interaction leads to M-C ≡ N-M ' structural damage, and then leads to collapsing for PBA three dimensional skeletal structure.So hole it is more and
Often cyclical stability is poor for PBA material when tool appraises at the current rate simultaneously there are two transition metal, leads to the circulation longevity of sodium-ion battery
It orders shorter.
In view of this, it is desirable to provide a kind of scheme can fundamentally solve the problems, such as that PBA three dimensional skeletal structure collapses, and improve
The cyclical stability of sodium-ion battery.
Summary of the invention
In view of the problems in the background art, the purpose of the present invention is to provide a kind of sodium-ion batteries, can improve
The cycle performance of sodium-ion battery.
In order to achieve the above object, the present invention provides a kind of sodium-ion batteries comprising anode strip, cathode sheets, isolation
Film and electrolyte, isolation film are arranged between cathode sheets and anode strip, and electrolyte includes non-aqueous organic solvent and is dissolved in
Sodium salt in non-aqueous organic solvent.The electrolyte further includes the additive being dissolved in non-aqueous organic solvent, the additive
Cation charge/radius ratio be less than sodium ion charge/radius ratio.Active material of cathode in the cathode sheets includes general
Shandong scholar's indigo plant class material.
Compared with the existing technology, the invention has the benefit that
Charge/radius ratio of the cation of electrolysis additive of the invention is less than charge/radius ratio of sodium ion, in sodium
The cation can preferentially be embedded in, deviate from prussian blue material in ion battery charge and discharge process, since the cation has
Lesser charge/radius ratio, so it is smaller to the structure destruction of prussian blue material during insertion, abjection, thus
The three dimensional skeletal structure that prussian blue material can be stablized makes sodium-ion battery have good cycle performance.
Detailed description of the invention
Fig. 1 is the cycle performance comparison diagram of embodiment 3 and the sodium-ion battery in comparative example 1.
Specific embodiment
The following detailed description of sodium-ion battery according to the present invention.
Sodium-ion battery according to the present invention includes anode strip, cathode sheets, isolation film and electrolyte, and isolation film setting exists
Between cathode sheets and anode strip, electrolyte includes non-aqueous organic solvent and the sodium salt that is dissolved in non-aqueous organic solvent.It is described
Electrolyte further includes the additive being dissolved in non-aqueous organic solvent, and charge/radius ratio of the cation of the additive is less than
Sodium ion charge/radius ratio (for).Active material of cathode in the cathode sheets includes prussian blue material.
Charge/radius ratio of the cation of electrolysis additive of the invention is less than charge/radius ratio of sodium ion, in sodium
The cation can preferentially be embedded in, deviate from prussian blue material in ion battery charge and discharge process, since the cation has
Lesser charge/radius ratio, so it is smaller to the structure destruction of prussian blue material during insertion, abjection, thus
The three dimensional skeletal structure that prussian blue material can be stablized makes sodium-ion battery have good cycle performance.
In sodium-ion battery of the present invention, charge/radius ratio range of the cation of the additive can beCharge is the valence state of ion.
In sodium-ion battery of the present invention, the cation of the additive can be selected from NH4 +、K+、 Rb+、Cs+In
It is one or more of.The anion of the additive can be selected from PF6 -、ClO4 -、BF4 -、 FSI-(double fluorine sulfimide roots), TFSI-
(double trifluoromethanesulfonimide roots), CF3SO3 -、DFOB-(difluoro oxalate borate), AlCl4 -、FeCl4 -、BCl4 -、POF4 -、
AsF6 -、SbF6 -One or more of.Preferably, the additive can be selected from ammonium hexafluorophosphate (NH4PF6), Potassium Hexafluorophosphate
(KPF6), potassium hyperchlorate (KClO4), hexafluorophosphoric acid rubidium (RbPF6), rubidium perchlorate (RbClO4), hexafluorophosphoric acid caesium (CsPF6), it is high
Cesium chlorate (CsClO4One or more of).
In sodium-ion battery of the present invention, the content of the additive can be the electrolyte gross mass
0.01%~20%.The additive amount of additive is excessive, and on the one hand will lead to it cannot be dissolved completely in electrolyte, on the other hand
The mobility of sodium ion can be reduced, to reduce the performance of sodium-ion battery；The additive amount of additive is very few, then does not have corresponding
Effect.Preferably, the content of the additive is the 1%~10% of the electrolyte gross mass.
In sodium-ion battery of the present invention, the type and content of the non-aqueous organic solvent is unrestricted, can root
It is selected according to actual demand.Preferably, the non-aqueous organic solvent can be selected from ethylene carbonate (EC), propene carbonate
(PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), glycol dimethyl ether, diethylene glycol two
Methyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran, ethyl methane sulfonate, dimethyl sulfite, sulfurous acid two
One or more of ethyl ester.
In sodium-ion battery of the present invention, the type and content of the sodium salt is unrestricted, can be according to practical need
It asks and is selected.Preferably, the sodium salt can be selected from sodium perchlorate (NaClO4), sodium hexafluoro phosphate (NaPF6), sodium tetrafluoroborate
(NaBF4), trifluoromethyl sulfonate (NaFSI), one or more of bis trifluoromethyl sodium sulfonate (NaTFSI).
In sodium-ion battery of the present invention, the electrolyte may also include film for additive.Specifically, it is described at
Film additive can be selected from one or both of fluorinated ethylene carbonate (FEC), 1,2- difluorinated ethylene carbonate (DFEC).At
Film additive be added can further stable sodium-ion battery electrode interface, improve the performance of sodium-ion battery.
In sodium-ion battery of the present invention, the molecular formula of the prussian blue material can beA is alkali or alkaline earth metal cation, and M is transition gold
Belonging to cation, M ' is transition-metal cation,For M ' (CN)6Hole, b-H2O is water of coordination, i-H2O is interstitial water, 0 < x≤
2,0 < c≤1,0 < y < 1,0≤z≤16.Preferably, A is selected from Li+、Na+、K+、Ca2+、Mg2+One of, M be selected from Mn, Fe, Co,
One or more of Ni, Cu, Zn cation, M ' are selected from one or more of Mn, Fe, Co, Ni, Cu, Zn cation.
In sodium-ion battery of the present invention, the type and content of the active material of positive electrode in the anode strip not by
Limitation, can be selected according to actual needs.Preferably, the active material of positive electrode can be selected from metallic sodium, carbon material, alloy
Material, excessively metal oxide, excessively one or more of plating metal sulfide, phosphorous-based materials, titanate material.The carbon materials
Material can be selected from one or more of graphite, soft carbon, hard carbon, the alloy material can be selected from by Si, Ge, Sn, Pb, Sb extremely
The alloy material of few two kinds of compositions, the alloy material is further selected to be made of at least one of Si, Ge, Sn, Pb, Sb and C
Alloy material, it is described cross metal oxide and it is described cross plating metal sulfide chemical formula be M1xNy, M1 can be selected from Fe,
One or more of Co, Ni, Cu, Mn, Sn, Mo, Sb, V, N are selected from O or S, and the phosphorous-based materials can be selected from red phosphorus, white phosphorus, black
One or more of phosphorus, the titanate material can be selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、 NaTi2
(PO4)3One or more of.
In sodium-ion battery of the present invention, the material of isolation film is unrestricted, can carry out according to actual needs
Selection.Preferably, isolation film can be selected from polypropylene screen, polyethylene film, polyethylene/polypropylene/polyethylene composite membrane, fiber
One or more of plain non-woven membrane, glass fibre membrane.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
1. the preparation of cathode sheets
By active material of cathodeIt is conductive
Agent acetylene black, binder polyvinylidene fluoride (PVDF) 80:10:10 in mass ratio fill in N-Methyl pyrrolidone dicyandiamide solution
Divide after being uniformly mixed, is coated on drying on Al foil, cold pressing, obtains cathode sheets.
2. the preparation of anode strip
By active material of positive electrode hard carbon, conductive agent acetylene black, binder polyacrylic acid 88:2:10 in mass ratio go from
After being thoroughly mixed in sub- aqueous solvent uniformly, it is coated on drying on Al foil, cold pressing, obtains anode strip.
3. the preparation of electrolyte
By suitable sodium hexafluoro phosphate (NaPF6) it is dissolved in that EC:PC:FEC=47.5:47.5:5 (volume ratio) is non-aqueous to be had
In solvent, it is made into NaPF6Concentration is the electrolyte of 1mol/L, and mass percentage is added on the basis of this electrolyte and is
0.5% ammonium hexafluorophosphate.
4. the preparation of sodium-ion battery
Battery core is made by winding in cathode sheets, anode strip and polypropylene isolation film, battery core is then packed into battery packages
In shell, prepared electrolyte is injected later, and the sodium-ion battery of embodiment 1 is made using techniques such as chemical conversion, standings.
Embodiment 2
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 1%.
Embodiment 3
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 2%.
Embodiment 4
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 10%.
Embodiment 5
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 20%.
Embodiment 6
Sodium-ion battery is prepared according to the method in embodiment 3, only by the cathode active material in cathode sheets preparation process
Material is changed to
Embodiment 7
Sodium-ion battery is prepared according to the method in embodiment 3, only by the anode activity material in anode strip preparation process
Material is changed to Sb/C.
Embodiment 8
Sodium-ion battery is prepared according to the method in embodiment 3, it only will be non-aqueous organic molten during electrolyte quota
Agent is changed to EC:DMC:FEC=47.5:47.5:5 (volume ratio).
Embodiment 9
Sodium-ion battery is prepared according to the method in embodiment 3, is only changed to the sodium salt during electrolyte quota
NaClO4。
Embodiment 10
Sodium-ion battery is prepared according to the method in embodiment 3, only by the isolation film in sodium-ion battery preparation process
It is changed to cellulosic nonwoven fabric film.
Embodiment 11
Sodium-ion battery is prepared according to the method in embodiment 3, only by the ammonium hexafluorophosphate during electrolyte quota
It is changed to Potassium Hexafluorophosphate.
Embodiment 12
Sodium-ion battery is prepared according to the method in embodiment 3, only by the ammonium hexafluorophosphate during electrolyte quota
It is changed to hexafluorophosphoric acid rubidium.
Embodiment 13
Sodium-ion battery is prepared according to the method in embodiment 3, only by the ammonium hexafluorophosphate during electrolyte quota
It is changed to hexafluorophosphoric acid caesium.
Embodiment 14
Sodium-ion battery is prepared according to the method in embodiment 3, it only will be non-aqueous organic molten during electrolyte quota
Agent is changed to EC:DMC:DEC=35:35:30 (volume ratio).
Comparative example 1
Sodium-ion battery is prepared according to the method in embodiment 1, does not add hexafluoro phosphorus during electrolyte quota only
Sour ammonium.
Comparative example 2
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 0.01%.
Comparative example 3
Sodium-ion battery is prepared according to the method in embodiment 1, only by the ammonium hexafluorophosphate during electrolyte quota
Additive amount be changed to 30%.
The cycle performance test of sodium-ion battery will be illustrated next.
At room temperature, sodium-ion battery embodiment 1~14 and comparative example 1~3 obtained is with 0.5C multiplying power constant-current charge
It is 4.0V to voltage, is then 0.1C with 4.0V constant-voltage charge to electric current, sodium-ion battery reaches fully charged state, Zhi Houjing at this time
5min is set, is 2.0V with 0.5C multiplying power constant-current discharge to voltage, then stand 5min, this is a cycle charge discharge electric process.
Capacity retention ratio (%)=sodium-ion battery n-th week circulation discharge capacity/sodium of the sodium-ion battery circulation after n weeks
Discharge capacity × 100% of ion battery the 1st week circulation.
In table 1, it can be seen that in the electrolyte of sodium-ion battery by the comparison of embodiment 1~14 and comparative example 1
It is added to after charge/radius ratio cation smaller than sodium ion, the cycle performance of sodium-ion battery has different degrees of mention
It is high.This is primarily due in sodium-ion battery charge and discharge process, and charge/radius ratio cation smaller than sodium ion replaces part
Sodium ion insertion is deviate from the structure of prussian blue material, and the three dimensional skeletal structure of prussian blue material is stabilized, thus
Improve the cycle performance of sodium-ion battery.Fig. 1 is the cycle performance comparison of embodiment 3 and the sodium-ion battery in comparative example 1
Figure.It will be seen from figure 1 that when not adding NH in electrolyte4 +When, the cycle performance of sodium-ion battery is poor, and circulation is after 40 weeks
Capacity retention ratio only has 35%；And as the NH for being added to 2% in electrolyte4 +Later, the cycle performance of sodium-ion battery obtains
It is obviously improved, capacity retention ratio of the circulation after 40 weeks has been increased to 84%.
It can be seen that by the comparison of Examples 1 to 5 and comparative example 2, comparative example 3 as NH in electrolyte4 +Content it is very low
When, the cycle performance of sodium-ion battery does not change substantially；As the NH in electrolyte4 +When content is too high, sodium-ion battery is followed
Ring performance is relatively low, this is primarily due to be added to excessive NH in electrolyte4 +Later, in electrolyte sodium ion mobility
Decline more, the cycle performance of sodium-ion battery is caused to decline.When preparing the electrolyte of comparative example 3, discovery has part six simultaneously
Fluorophosphoric acid ammonium is insoluble, therefore the content of ammonium hexafluorophosphate should not be too high.When in electrolyte charge/radius ratio it is smaller than sodium ion from
When sub- content is fallen in preferred section, the cycle performance of sodium-ion battery improves most.
It can be seen that by the comparison of embodiment 3 and embodiment 14 after adding film for additive FEC in the electrolytic solution,
Can further stable sodium-ion battery electrode interface, further increase the cycle performance of sodium-ion battery.
In conclusion adding charge/radius ratio sun smaller than sodium ion in the electrolyte of the sodium-ion battery of the application
After ion, can effectively stable prussian blue material three dimensional skeletal structure, make sodium-ion battery have good cyclicity
Energy.
Claims (10)
1. a kind of sodium-ion battery, comprising:
Anode strip；
Cathode sheets；
Isolation film is arranged between cathode sheets and anode strip；And
Electrolyte, including non-aqueous organic solvent and the sodium salt being dissolved in non-aqueous organic solvent；
It is characterized in that,
The electrolyte further includes the additive being dissolved in non-aqueous organic solvent, charge/half of the cation of the additive
Charge/radius ratio of the diameter than being less than sodium ion；
Active material of cathode in the cathode sheets includes prussian blue material.
2. sodium-ion battery according to claim 1, which is characterized in that charge/radius of the cation of the additive
The range of ratio is
3. sodium-ion battery according to claim 2, which is characterized in that the cation of the additive is selected from NH4 +、K+、
Rb+、Cs+One or more of.
4. sodium-ion battery according to claim 3, which is characterized in that the anion of the additive is selected from PF6 -、
ClO4 -、BF4 -、FSI-、TFSI-、CF3SO3 -、DFOB-、AlCl4 -、FeCl4 -、BCl4 -、POF4 -、AsF6 -、SbF6 -One of or
It is several.
5. sodium-ion battery according to claim 1, which is characterized in that the content of the additive is that the electrolyte is total
The 0.01%~20% of quality, it is preferable that the content of the additive is the 1%~10% of the electrolyte gross mass.
6. sodium-ion battery according to claim 1, which is characterized in that the non-aqueous organic solvent is selected from ethylene carbonate
Ester, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, glycol dimethyl ether, diethylene glycol dimethyl ether, three
Glycol dimethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran, ethyl methane sulfonate, dimethyl sulfite, in sulfurous acid diethyl ester
It is one or more of.
7. sodium-ion battery according to claim 1, which is characterized in that the sodium salt is selected from sodium perchlorate, hexafluorophosphoric acid
One or more of sodium, sodium tetrafluoroborate, trifluoromethyl sulfonate, bis trifluoromethyl sodium sulfonate.
8. sodium-ion battery according to claim 1, which is characterized in that the electrolyte further includes film for additive, institute
It states film for additive and is selected from one or both of fluorinated ethylene carbonate, 1,2- difluorinated ethylene carbonate.
9. sodium-ion battery according to claim 1, which is characterized in that the molecular formula of the prussian blue material isA is alkali or alkaline earth metal cation, and M is transition gold
Belonging to cation, M ' is transition-metal cation,For M ' (CN)6Hole, b-H2O is water of coordination, i-H2O is interstitial water, 0 < x≤
2,0 < c≤1,0 < y < 1,0≤z≤16.
10. sodium-ion battery according to claim 1, which is characterized in that the active material of positive electrode choosing in the anode strip
From in metallic sodium, carbon material, alloy material, mistake metal oxide, mistake plating metal sulfide, phosphorous-based materials, titanate material
One or more.
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| CN112723384A (en) * | 2020-12-25 | 2021-04-30 | 电子科技大学 | Composite manganese-iron-based Prussian blue material and preparation method and application thereof |
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