CN107275672A - It is a kind of containing rubidium and/or the sodium-ion battery electrolysis additive of caesium cation and its application - Google Patents
It is a kind of containing rubidium and/or the sodium-ion battery electrolysis additive of caesium cation and its application Download PDFInfo
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- CN107275672A CN107275672A CN201710656500.4A CN201710656500A CN107275672A CN 107275672 A CN107275672 A CN 107275672A CN 201710656500 A CN201710656500 A CN 201710656500A CN 107275672 A CN107275672 A CN 107275672A
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Abstract
The invention discloses a kind of containing rubidium and/or the sodium-ion battery electrolysis additive of caesium cation and its application.A kind of application the invention provides rubidium and/or caesium cation in sodium-ion battery field as sodium-ion battery electrolysis additive, wherein, described sodium-ion battery electrolyte includes rubidium and/or caesium cation, electrolyte sodium salt and organic solvent；Molar concentration of the described rubidium and/or caesium cation in described sodium-ion battery electrolyte is 0.01 0.2mol/L；Molar concentration of the described electrolyte sodium salt in described sodium-ion battery electrolyte is 0.5 2mol/L.Sodium-ion battery electrolysis additive containing rubidium and/or caesium cation is applied to sodium-ion battery field by the present invention, is further increased the stability of sodium-ion battery negative pole SEI films, the polarization for reducing impedance, reducing sodium-ion battery, is improved the stable circulation performance of sodium-ion battery, extends the sodium-ion battery life-span.
Description
Technical field
The invention belongs to sodium-ion battery field, and in particular to a kind of sodium-ion battery electricity containing rubidium and/or caesium cation
Solve solution additive and its application.
Background technology
In recent years, because the haze that environmental pollution, greenhouse effects induce turns into the important hidden danger of national health, energy-conservation subtracts
Row, green energy resource are increasingly becoming the important means for solving problem of environmental pollution.Traditional fossil energy during use not
Only pollute the environment, and belong to the non-renewable energy, people increasingly pay attention to renewable to water energy, solar energy, wind energy etc.
The development and utilization of the energy.But these energy have randomness, intermittent feature, it is impossible to which it to be directly accessed by people power network
With, it is necessary to converted by energy-storage system, therefore efficiently easily energy storage technology is worldwide research heat at present for development
Point.
Lithium ion battery is because of its high-energy-density, good cycle performance and high operating voltage, in major portables
Field of power supplies application.But lithium resource is increasingly short, price is gradually increasing, make novel low-cost and can large-scale application sodium from
Sub- secondary cell arises at the historic moment.In view of sodium and lithium have similar physical and chemical performance, sodium-ion battery is comprehensive effect of future generation
The excellent energy-storage battery new system of energy.
Relative to lithium ion battery, sodium-ion battery is widely distributed, carry because its sodium resource is than lithium resource reserves very abundant
Refining is simple, and cost will be substantially reduced.But at the same time, the electrode potential of metallic sodium is compared with the 0.34V that is higher by of lithium, and sodium-ion battery
There is also defect, the relative atomic mass of such as sodium element is more much higher than lithium, causes theoretical specific capacity small, and the 1/2 of not enough lithium.Sodium
Ratio of ionic radii lithium ion radius is big so that sodium ion insertion in battery material is more difficult to abjection.The stone in lithium ion battery
Ink is as negative pole, with preferable chemical property, but uses conventional carbonates electrolyte, and sodium ion can not be orderly
Embedded abjection in an orderly manner in graphite cathode, and hard carbon is as a kind of unordered carbon material, is the main negative pole material of sodium-ion battery
Material.
By taking lithium ion battery as an example, solid electrolyte interface (Solid Electrolyte Interface, SEI) film shape
Into during liquid lithium ionic cell first charge-discharge, electrode material reacts with electrolyte on solid-liquid phase interface, shape
Into one layer of passivation layer for being covered in electrode material surface, this passivation layer is a kind of boundary layer, the feature with solid electrolyte,
It is electronic body, is Li+Excellence conductor, Li+Can and abjection freely embedded by the passivation layer, this layer of passivating film
As SEI films.The formation of SEI films produces vital influence to the performance of electrode material.On the one hand, the formation of SEI films disappears
Consume part lithium ion so that the increase of first charge-discharge irreversible capacity, reduce the efficiency for charge-discharge of electrode material；The opposing party
Face, SEI films have organic solvent insoluble, can be stabilized in organic electrolyte solution, and solvent molecule can not pass through
This layer of passivating film, so as to effectively prevent the common insertion of solvent molecule, it is to avoid insertion is made to electrode material altogether because of solvent molecule
Into destruction, thus substantially increase the cycle performance and service life of electrode.The formation of SEI films efficiently separated electrolyte with
The direct contact of electrode, makes electrolyte will not continue to decompose in electrode interface redox.SEI films are thinner and more form compact and stable,
The cycle life of battery can be more greatly promoted, the internal resistance of battery is reduced.
Therefore, the formation mechenism of further investigation SEI films, composition structure, stability and its influence factor, and further find
Improve the effective way of SEI film properties, always be the focus of the electrochemical educational circles's research in the world.Existing improvement SEI film properties
One of technological means, is exactly to add distinctive film for additive in the electrolytic solution, including organic film for additive and inorganic film forming
Additive.Organic film for additive is mainly first reduced instead of organic solvent, is formed SEI films, is thus inhibited electrolyte
Decomposition, improve the life-span of battery；And inorganic film for additive mainly includes chemical reaction type, electrochemical reduction type and SEI
Film modified type three types.
Fluorochemical is the main sodium-ion battery electrolysis additive of a class, and pertinent literature ACS is had at present
Appl.Mater.Interfaces, 2011,3,4165-4168 and the A of Chinese patent application CN 103493279 report fluorine-containing
Compound can be effectively in negative pole formation SEI films.
Rubidium and/or caesium cation as doped chemical lithium ion cell positive exploitation (CN105609758 A) and lithium from
(A of CN 106450452) has been applied in sub- battery high-voltage electrolyte exploitation.But not yet have rubidium and/or caesium cation at present
The report of related application in sodium-ion battery field.
The content of the invention
The technical problems to be solved by the invention are further to improve the circulation of sodium-ion battery in the prior art
Stability and battery life, thus the answering in sodium-ion battery electrolyte is prepared there is provided a kind of rubidium and/or caesium cation
With.Sodium-ion battery electrolysis additive containing rubidium and/or caesium cation is applied to sodium-ion battery field by the present invention, enters one
Step improves the stability of sodium-ion battery negative pole SEI films, reduces impedance, so as to reduce the polarization of sodium-ion battery, carry
The high stable circulation performance of sodium-ion battery, extend the sodium-ion battery life-span.
The main research experience for using for reference lithium-ion battery electrolytes of exploitation of current organic system sodium-ion battery electrolyte, collection
In in carbonates system.But the additive being applicable in lithium ion battery is not necessarily applied to sodium-ion battery, such as additive
Vinylene carbonate (VC) can increase the cyclical stability of lithium ion battery, but be run counter to desire in sodium-ion battery.Therefore lithium
Experience in ion battery can not be covered in sodium-ion battery completely, and sodium-ion battery electrolyte system also needs to further complete
Kind and exploitation.The present inventor is devoted for years in sodium-ion battery research field, especially in sodium-ion battery electrolyte
Exploitation in terms of carried out the work of a large amount of in-depth studies.Tested by a series of creative research and development, inventor has found：In sodium
Rubidium and/or caesium cation are added in ion battery electrolyte can change negative pole SEI membrane structures and composition, so as to improve sodium ion
The stable circulation performance and battery life of battery.
The present invention is to solve above-mentioned technical problem by following technical proposals.
Sodium-ion battery electrolyte is used as in sodium-ion battery field the invention provides a kind of rubidium and/or caesium cation
The application of additive, wherein, described sodium-ion battery electrolyte includes rubidium and/or caesium cation, electrolyte sodium salt and had
Machine solvent；Molar concentration of the described rubidium and/or caesium cation in described sodium-ion battery electrolyte is 0.01-
0.2mol/L；Molar concentration of the described electrolyte sodium salt in described sodium-ion battery electrolyte is 0.5-2mol/L.
In the present invention, when including rubidium or caesium cation in described sodium-ion battery electrolyte, described rubidium and/or caesium
The molar concentration of cation wherein refers to the concentration of single rubidium or caesium cation.When bag in described sodium-ion battery electrolyte
Containing rubidium and during caesium cation, the molar concentration of described rubidium and/or caesium cation wherein refers to both concentration summations, and two
Person's proportioning is not required to carry out any restriction.
In the present invention, described rubidium cation can exist in the form of its salt is rubidium salt；Described caesium cation can be with
Exist in the form of its salt is cesium salt.
Specifically, the invention provides a kind of described rubidium salt and/or cesium salt in sodium-ion battery field as sodium from
The application of the SEI film for additive of sub- battery electrolyte.
In the present invention, described rubidium salt be refer to dissociate in described sodium-ion battery electrolyte environment rubidium sun from
The inorganic rubidium salt and/or organic rubidium salt of son.Wherein, described inorganic rubidium salt is preferably selected from hexafluorophosphoric acid rubidium (RbPF6), perchloric acid
Rubidium (RbClO4), rubidium nitrate (RbNO3) and rubidium carbonate (Rb2CO3) in one or more；Described organic rubidium salt is preferably selected from
Bis trifluoromethyl sulfimide rubidium (RbTFSI), trifluoromethanesulfonic acid rubidium (RbCF3SO3), difluoro oxalate boric acid rubidium (RbC2BF2O4)、
Dioxalic acid boric acid rubidium (RbC4BO8) and methanesulfonic acid rubidium (RbCH3SO3) in one or more.It is further preferably described in the present invention
Rubidium salt be hexafluorophosphoric acid rubidium (RbPF6) and/or bis trifluoromethyl sulfimide rubidium (RbTFSI).
In the present invention, described cesium salt be refer to dissociate in described sodium-ion battery electrolyte environment caesium sun from
The inorganic cesium salt and/or organic cesium salt of son.Wherein, described inorganic cesium salt is preferably selected from hexafluorophosphoric acid caesium (CsPF6), perchloric acid
Caesium (CsClO4), cesium nitrate (CsNO3) and cesium carbonate (Cs2CO3) in one or more；Described organic cesium salt is preferably selected from
Bis trifluoromethyl sulfimide caesium (CsTFSI), trifluoromethanesulfonic acid caesium (CsCF3SO3), difluoro oxalate boric acid caesium (CsC2BF2O4)、
Dioxalic acid boric acid caesium (CsC4BO8) and methanesulfonic acid caesium (CsCH3SO3) in one or more.It is further preferably described in the present invention
Cesium salt be hexafluorophosphoric acid caesium (CsPF6) and/or bis trifluoromethyl sulfimide caesium (CsTFSI).
When heretofore described rubidium cation exists with rubidium salt form, described caesium cation exists in cesium salt form
When, the molar concentration of described rubidium salt and/or cesium salt in described sodium-ion battery electrolyte and described rubidium and/or caesium sun
The molar concentration of ion wherein is consistent.I.e. in the present invention, described rubidium salt and/or cesium salt are in described sodium-ion battery
Molar concentration in electrolyte is preferably 0.025-0.1mol/L, such as 0.05mol/L.
Wherein, described electrolyte sodium salt can be the electricity used in sodium-ion battery electrolyte routine in sodium-ion battery field
Matter sodium salt is solved, heretofore described electrolyte sodium salt may be selected from NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3、Na
(CF3SO2)2N、NaBCl4、NaNO3、NaPOF4、NaSCN、NaCN、NaAsF6、NaTaF6、NaCF3CO2、NaSbF6、NaC6H5CO2、
Na(CH3)C6H4SO3、NaHSO4With NaB (C6H5)4In one or more, further preferred NaPF6、NaClO4、NaSO3CF3With
Na(CH3)C6H4SO3In one or more, still more preferably NaClO4And/or NaPF6。
Wherein, molar concentration of the described electrolyte sodium salt in described sodium-ion battery electrolyte is preferably 0.6-
1.2mol/L, further preferred 0.8-1.0mol/L.
Wherein, described organic solvent can be having used in the sodium-ion battery electrolyte routine in sodium-ion battery field
Machine solvent.Heretofore described organic solvent can include carbonic ester, and described carbonic ester is preferably cyclic carbonate and/or chain
Shape carbonic ester；Described cyclic carbonate is preferably selected from propene carbonate (PC), ethylene carbonate (EC) and butylene carbonate fat
(BC) one or more in；Described linear carbonate is preferably selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), carbon
Sour methyl ethyl ester (EMC), methyl propyl carbonate (MPC), methyl formate (MF), Ethyl formate (EF), methyl acetate (MA), ethyl acetate
And the one or more in ethyl propionate (EP) (EA).
In the present invention, described organic solvent also can further include other solvents, and other described solvents may be selected from four
One in hydrogen furans (THF), dioxolane (DOL), diethyl glycol dimethyl ether (DG), acetonitrile (AN) and dimethyl sulfoxide (DMSO)
Plant or a variety of.
In the present invention, the volumn concentration of all kinds of solvent compositions is that this area is conventional in described organic solvent.Its
In, the volumn concentration of described cyclic carbonate is preferably 20%-100%, more preferably 40%-80%.It is described
(linear carbonate+other solvents) volumn concentration preferred 0%-80%, more preferably 20%-60%；Wherein,
The volumn concentration that described linear carbonate accounts for described (linear carbonate+other solvents) is preferably 20%-100%,
More preferably 60%-100%；Other described solvents account for the volume basis of described (linear carbonate+other solvents)
Content is preferably 0%-80%, more preferably 0%-40%.The volumn concentration of each component in described organic solvent
The cumulative volume of the organic solvent of the volume of each component in organic solvent described in=100%*/described.
In one particular embodiment of the present invention, described organic solvent is made up of PC, EC, and its volume ratio is preferably 4:
1。
In one particular embodiment of the present invention, described organic solvent is made up of PC, DMC, and its volume ratio is preferably
1:4。
In one particular embodiment of the present invention, described organic solvent is made up of PC, EC and DEC, and its volume ratio is excellent
Elect 4 as:1:5.
In one particular embodiment of the present invention, described organic solvent is made up of PC, EC and DMC, and its volume ratio is excellent
Elect 4 as:1:5.
In one particular embodiment of the present invention, described organic solvent is made up of PC, AN and EMC, and its volume ratio is excellent
Elect 4 as:1:5.
In the present invention, described sodium-ion battery electrolyte may also include except described rubidium and/or caesium cation or described
Rubidium salt and/or cesium salt beyond other sodium-ion battery electrolysis additives.
Wherein, other described sodium-ion battery electrolysis additives can be the sodium used in routine in sodium-ion battery field
Ion battery electrolysis additive, is generally comprised in SEI cathode film formations additive, additives for overcharge protection additive, control electrolyte
Water and the additive of HF contents, additive, flame-retardant additive, conductive additive and the multifunction additive of improvement high temperature performance
Deng.Other heretofore described sodium-ion battery electrolysis additives can be SEI cathode film formation additives, further can be containing
Fluorine class SEI cathode film formation additives, described fluorinated SEI cathode film formation additives may be selected from fluorinated ethylene carbonate (FEC),
The phosphonitrile (EPFP) of five fluorine ring of ethyoxyl three, difluoroethylene carbonate (DFEC) and three (2,2,2- trifluoroethyls) phosphates
(TFP) one or more in.
In the present invention, when described sodium-ion battery electrolyte also includes other sodium-ion battery electrolysis additives,
The percentage composition of other described sodium-ion battery electrolysis additives can be conventional used, the present invention in sodium-ion battery field
Described in percentage composition can be 0.5%-8%, or for 1%-6%, or be 2%-5%.Described percentage composition refers to described
Other sodium-ion battery electrolysis additives percentage of the quality in described sodium-ion battery electrolyte gross mass.
In one particular embodiment of the present invention, described sodium-ion battery electrolyte is by described rubidium salt and/or caesium
Salt, described electrolyte sodium salt, and described organic solvent composition.
In one particular embodiment of the present invention, described sodium-ion battery electrolyte is by described rubidium salt and/or caesium
Salt, other described sodium-ion battery electrolysis additives, described electrolyte sodium salt, and described organic solvent composition.
Present invention also offers a kind of sodium-ion battery electrolyte, it includes rubidium and/or caesium cation, electrolyte sodium salt,
And organic solvent, alternatively also include other sodium-ion battery electrolysis additives；Wherein, described rubidium and/or caesium sun from
Sub, described electrolyte sodium salt, described organic solvent, other described sodium-ion battery electrolysis additives are such as preceding institute
State.
In one particular embodiment of the present invention, described sodium-ion battery electrolyte is by described rubidium and/or caesium sun
Ion, other described sodium-ion battery electrolysis additives, described electrolyte sodium salt, and described organic solvent group
Into.
Present invention also offers a kind of preparation method of sodium-ion battery electrolyte, it uses electrolyte in this area conventional
Preparation method is carried out.Preferred its of the invention is comprised the steps of：Added in organic solvent as described above as described above
Electrolyte sodium salt and sodium-ion battery electrolysis additive as described above, it is well mixed,；Or, as described above
Electrolyte sodium salt as described above, rubidium salt as described above and/or cesium salt and as described above other are added in organic solvent
Sodium-ion battery electrolysis additive, it is well mixed,.
Present invention also offers a kind of sodium-ion battery electrolysis additive, it includes rubidium and/or caesium cation or rubidium salt
And/or cesium salt, alternatively also include other sodium-ion battery electrolysis additives；Wherein, described rubidium and/or caesium cation,
Described rubidium salt and/or cesium salt, other described sodium-ion battery electrolysis additives are as previously described.
In one particular embodiment of the present invention, described sodium-ion battery electrolysis additive is by described rubidium salt
And/or cesium salt and at least one described other sodium-ion battery electrolysis additives composition；Wherein, other described sodium ions
Battery electrolyte additive is preferably fluorinated SEI negative pole cathode film formation additives, more preferably FEC and/or EPFP.
Present invention also offers a kind of sodium-ion battery electrolysis additive as described above or sodium ion as described above
Application of the battery electrolyte in sodium-ion battery field.
Present invention also offers a kind of sodium-ion battery, it includes positive plate, negative plate, barrier film and electrolyte；Its
In, the cathode film containing positive electrode active materials that described positive plate includes plus plate current-collecting body and is arranged on plus plate current-collecting body
Piece；Described negative plate includes negative current collector and the negative electrode film containing negative active core-shell material being arranged on negative current collector
Piece；Described barrier film is interval between positive plate and negative plate；Described electrolyte is sodium-ion battery as described above electricity
Solve liquid.
Wherein, described positive electrode active materials are conventional used in sodium-ion battery field, including can deviate from, receive sodium from
The material of son；The present invention is preferably sodium compound transition metal oxide.Wherein, described sodium compound transition metal oxide is preferred
Added for sodium transition metal oxide, sodium transition metal oxide in the compound that other transition metal or nontransition metal are obtained
One or more, further preferred sodium cobalt/cobalt oxide, sodium manganese oxide, sodium Quito element/transition metal compound, transition metal
One or more in sodium ascorbyl phosphate and transition metal fluorophosphoric acid sodium salt；Still more preferably it is NaxCoO2、NaxMnO2、
NaNi0.33Fe0.33Mn0.33O2、NaFePO4、NaCoPO4、NaVPO4In one or more.
In the present invention, described negative active core-shell material is conventional used in sodium-ion battery field, including can receive, deviate from
The material of sodium ion.In the present invention can for hard carbon, acetylene black, sodium titanate and can with sodium formation alloy metal in one kind or
It is a variety of.
Wherein, it in sodium-ion battery field in the barrier film used in routine, the present invention can be PP/ that described barrier film, which can be,
PE barrier films and fibreglass diaphragm.
The sodium-ion battery of the present invention further may also include battery outer packing.
Present invention also offers a kind of preparation method of described sodium-ion battery, it uses sodium-ion battery in this area
The conventional method of preparation is carried out.Preferred its of the invention is comprised the steps of：By positive plate, barrier film, negative plate in order
Fold, centre of the barrier film in positive plate and negative plate is played buffer action, stacking afterwards obtains naked battery core, by naked battery core
It is placed in outer packing, injects sodium-ion battery electrolyte as described above and encapsulate, be melted into, you can.
Unless otherwise instructed, it is organic molten described in volumn concentration=100%* of each component in described organic solvent
The cumulative volume of the organic solvent of the volume of each component in agent/described；The weight/mass percentage composition of each component in described additive=
The gross mass of the sodium-ion battery electrolyte of the quality of each component in additive described in 100%*/described.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, and produce each preferable reality of the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：The present invention regard rubidium and/or caesium cation as sodium-ion battery electricity first
Solve solution additive and be applied to sodium-ion battery field, rubidium and/or caesium cation of the invention can cooperate with other sodium-ion batteries
Electrolysis additive, organic solvent or electrolyte sodium salt, help the hard carbon cathode surface of sodium-ion battery to form finer and close, more
Plus stable SEI films, so as to further improve the stability of sodium-ion battery negative pole SEI films, reduction impedance, reduce sodium ion electricity
The polarization in pond, the stable circulation performance for improving sodium-ion battery, extension sodium-ion battery life-span.
Brief description of the drawings
Fig. 1 is embodiment 1,1 metallic sodium of embodiment 2 and comparative example/hard carbon button cell cycle performance comparison diagram.
Fig. 2 is that the polarization ratio after embodiment 1, embodiment 2 and the circulating battery 100 of comparative example 1 circle is relatively schemed.
Fig. 3 is the impedance comparison figure after embodiment 1, embodiment 2 and the circulating battery 100 of comparative example 1 circle.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
Prepare embodiment：
Embodiment 1
PC and EC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, RbPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 2
PC and EC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, CsPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 3
PC, EC and DEC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbPF6Concentration be 0.05mol/L, NaPF6's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 4
PC, EC and DEC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsPF6Concentration be 0.05mol/L, NaPF6's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 5
PC, EC and DEC are well mixed, RbTFSI stirring and dissolvings is added, adds NaPF6, FEC is eventually adding, is stirred
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbTFSI concentration is 0.05mol/L,
NaPF6Concentration be 0.8mol/L, (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 6
PC, EC and DEC are well mixed, CsTFSI stirring and dissolvings is added, adds NaPF6, FEC is eventually adding, is stirred
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsTFSI concentration is 0.05mol/L,
NaPF6Concentration be 0.8mol/L, (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 7
PC, EC and DEC are well mixed, RbTFSI stirring and dissolvings is added, adds NaPF6, FEC is eventually adding, is stirred
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbTFSI concentration is 0.025mol/L,
NaPF6Concentration be 1.0mol/L, (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 8
PC, EC and DEC are well mixed, CsTFSI stirring and dissolvings is added, adds NaPF6, FEC is eventually adding, is stirred
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsTFSI concentration is 0.025mol/L,
NaPF6Concentration be 1.0mol/L, (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 9
PC and EC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, EPFP is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, RbPF6Concentration be 0.05mol/L, NaPF6Concentration be
1.0mol/L, EPFP weight/mass percentage composition are 1% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 10
PC and EC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, EPFP is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, CsPF6Concentration be 0.05mol/L, NaPF6Concentration be
1.0mol/L, EPFP weight/mass percentage composition are 1% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 11
PC, EC and DEC are well mixed, RbPF is added6Stirring and dissolving, adds NaClO4, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbPF6Concentration be 0.05mol/L, NaClO4's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 5% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 12
PC, EC and DEC are well mixed, CsPF is added6Stirring and dissolving, adds NaClO4, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsPF6Concentration be 0.05mol/L, NaClO4's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 5% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 13
PC, AN and EMC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, AN and EMC volume ratio are 4:1:5, RbPF6Concentration be 0.05mol/L, NaPF6's
Concentration is 1.0mol/L, and FEC weight/mass percentage composition is 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 14
PC, AN and EMC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, AN, EMC volume ratio are 4:1:5, CsPF6Concentration be 0.05mol/L, NaPF6It is dense
Spend for 1.0mol/L, FEC weight/mass percentage composition is 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 15
PC and EC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, RbPF6Concentration be 0.01mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 16
PC and EC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, CsPF6Concentration be 0.01mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 17
PC, EC and DEC are well mixed, RbPF is added6Stirring and dissolving, adds NaClO4, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbPF6Concentration be 0.2mol/L, NaClO4's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 5% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 18
PC, EC and DEC are well mixed, CsPF is added6Stirring and dissolving, adds NaClO4, FEC is eventually adding, is stirred molten
Solution produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsPF6Concentration be 0.2mol/L, NaClO4's
Concentration is 0.8mol/L, and FEC weight/mass percentage composition is 5% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 19
PC and EC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, RbPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.5mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 20
PC and EC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and EC volume ratio is 4:1, CsPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.5mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 21
PC, EC and DEC are well mixed, RbPF is added6Stirring and dissolving, adds NaTFSI, is eventually adding FEC, stirring
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, RbPF6Concentration be 0.025mol/L,
NaTFSI concentration is 2.0mol/L, and (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 22
PC, EC and DEC are well mixed, CsPF is added6Stirring and dissolving, adds NaTFSI, is eventually adding FEC, stirring
Dissolving produces required electrolyte.Wherein PC, EC and DEC volume ratio are 4:1:5, CsPF6Concentration be 0.025mol/L,
NaTFSI concentration is 2.0mol/L, and (additive quality accounts for the percentage of electrolyte gross mass for 2% for FEC weight/mass percentage composition
Than).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 23
PC and DMC are well mixed, RbPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and DMC volume ratio is 1:4, RbPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 24
PC and DMC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, FEC is eventually adding, stirring and dissolving is
Electrolyte needed for obtaining.Wherein PC and DMC volume ratio is 1:4, CsPF6Concentration be 0.05mol/L, NaPF6Concentration be
0.8mol/L, FEC weight/mass percentage composition are 2% (additive quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Embodiment 25
PC and EC are well mixed, CsPF is added6Stirring and dissolving, adds NaPF6, stirring and dissolving produces required electrolyte.
Wherein PC and EC volume ratio is 4:1, CsPF6Concentration be 0.05mol/L, NaPF6Concentration be 0.8mol/L.
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 1
Rubidium salt and/or cesium salt are free of in this comparative example.
PC and EC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Wherein PC
Volume ratio with EC is 4:1, NaPF6Concentration be 0.8mol/L, (additive quality accounts for electricity for 2% for FEC weight/mass percentage composition
Solve the percentage of liquid gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 2
Rubidium salt and/or cesium salt are free of in this comparative example.
PC, EC and DEC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Its
Middle PC, EC and DEC volume ratio are 4:1:5, NaPF6Concentration be 0.8mol/L, FEC weight/mass percentage composition is 2% (addition
Agent quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 3
Rubidium salt and/or cesium salt are free of in this comparative example.
PC and EC are well mixed, NaPF is added6, EPFP is eventually adding, stirring and dissolving produces required electrolyte.Wherein PC
Volume ratio with EC is 4:1, NaPF6Concentration be 1.0mol/L, (additive quality accounts for for 1% for EPFP weight/mass percentage composition
The percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 4
Rubidium salt and/or cesium salt are free of in this comparative example.
PC, EC and DEC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Its
Middle PC, EC and DEC volume ratio are 4:1:5, NaClO4Concentration be 0.8mol/L, FEC weight/mass percentage composition (adds for 5%
Plus agent quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 5
Rubidium salt and/or cesium salt are free of in this comparative example.
PC, AN and DEC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Its
Middle PC, AN and DEC volume ratio are 4:1:5, NaPF6Concentration be 1.0mol/L, FEC weight/mass percentage composition is 2% (addition
Agent quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 6
Rubidium salt and/or cesium salt are free of in this comparative example.
PC and EC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Wherein PC
Volume ratio with EC is 4:1, NaPF6Concentration be 0.5mol/L, (additive quality accounts for electricity for 2% for FEC weight/mass percentage composition
Solve the percentage of liquid gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 7
Rubidium salt and/or cesium salt are free of in this comparative example.
PC, EC and DEC are well mixed, NaTFSI is added, is eventually adding FEC, stirring and dissolving produces required electrolyte.Its
Middle PC, EC and DEC volume ratio are 4:1:5, NaTFSI concentration is 2.0mol/L, and FEC weight/mass percentage composition (adds for 2%
Plus agent quality accounts for the percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 8
Rubidium salt and/or cesium salt are free of in this comparative example.
PC and DMC are well mixed, NaPF is added6, FEC is eventually adding, stirring and dissolving produces required electrolyte.Wherein PC
Volume ratio with DMC is 1:4, NaPF6Concentration be 0.8mol/L, (additive quality accounts for for 2% for FEC weight/mass percentage composition
The percentage of electrolyte gross mass).
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Comparative example 9
Rubidium salt and/or cesium salt are free of in this comparative example.
PC and EC are well mixed, NaPF is added6, stirring and dissolving produces required electrolyte.Wherein PC and EC volume ratio
For 4:1, NaPF6Concentration be 0.8mol/L.
Sodium-ion battery is assembled into above-mentioned electrolyte, using metallic sodium as to electrode, active material hard carbon is working electrode,
Fibreglass diaphragm, assembles CR2016 button cells.
Effect example 1：
The sodium ion electricity prepared under the pattern of 0.1C rate charge-discharges to above-described embodiment 1-25 and comparative example 1-9
Pond is tested, and discharge cut-off voltage is 0.01V, and charge cutoff voltage is 2V.It is prepared by above-described embodiment 1-25 and comparative example 1-9
Capability retention after obtained sodium-ion battery electrolyte constituent and the circle of circulation 100 is as shown in table 1.
Table 1：After embodiment 1-25 and comparative example 1-9 sodium-ion battery electrolyte constituent and the circle of circulation 100
Capability retention
Data analysis in upper table is understood：
1st, on the premise of other conditions are consistent in control sodium-ion battery electrolyte, the reality of rubidium salt and/or cesium salt is added
Apply comparative example of the capability retention after a 1-25 circulation 100 is enclosed all than being not added with rubidium salt and/or cesium salt under same experimental conditions
1-9's will height.
2nd, the polarization of battery can be effectively reduced by adding the rubidium salt and/or cesium salt of finite concentration scope, improve the longevity of battery
Life, but is below or does not reach expected effect then higher than this concentration range.When the molar concentration of the rubidium cesium compound of addition
Less than 0.01mol/L, the effect of film for additive will not had；And if the viscosity of electrolyte can be influenceed higher than 0.2mol/L,
So as to cause the electrical conductivity of electrolyte to decline, ion transport capability is influenceed.
3rd, the molar concentration of electrolyte sodium salt also has an impact to battery performance.When the molar concentration of the electrolyte sodium salt of addition
Less than 0.5mol/L, it will the ionic conduction in influence battery；And if above 2mol/L, then can increase the viscosity of electrolyte,
Reduce the electrical conductivity of electrolyte.
4th, it can be seen from the data comparison of embodiment 25 and comparative example 9：In the sodium-ion battery electricity without any additive
Solve and 0.05M CsPF are added in liquid6Afterwards, the capability retention after the circle of sodium-ion battery circulation 100 can be made to be promoted to from 38.7%
85.8%.
5th, Fig. 1 is embodiment 1,1 metallic sodium of embodiment 2 and comparative example/hard carbon button cell cycle performance comparison diagram.From figure
In 1 it can be seen that embodiment 1 and embodiment 2 are after 100 circle circulations, capability retention is all more than 95%, and comparative example 1
Capability retention there was only 80.6%, illustrate to add after rubidium salt and/or cesium salt, the cyclical stability of battery increases.
Effect example 2：
By the battery of embodiment 1, embodiment 2 and comparative example 1, voltage, with 0.1C electric current, enters between 0.01V-2V
Row charge and discharge cycles.Fig. 2 is that the polarization ratio after embodiment 1, embodiment 2 and the circulating battery 100 of comparative example 1 circle is relatively schemed.Can from Fig. 2
To find out embodiment 1 and embodiment 2 after 100 circle circulations, the polarization of battery has obvious reduction relative to comparative example 1,
Illustrate that polarization of the battery in cyclic process can be reduced by adding rubidium salt and/or cesium salt battery, and then improve the life-span of battery.
Effect example 3：
It is starting voltage by the battery open circuit voltage of embodiment 1, embodiment 2 and comparative example 1, high frequency is 100000Hz, low
Frequency is 0.01Hz, and testing impedance is carried out on CHI760E electrochemical workstations.Fig. 3 is embodiment 1, embodiment 2 and comparative example 1
Impedance comparison figure after the circle of circulating battery 100.Wherein, Z represents impedance, and ohm represents unit ohm.As can be seen from Figure 3 it is real
Example 1 and embodiment 2 are applied after 100 circle circulations, the impedance of battery has obvious reduction relative to comparative example 1, and then verifies
Fig. 1, Fig. 2 result.
Above-described embodiment is only the preferred embodiments of the invention, but the present invention is not limited in above-described embodiment, not
The corresponding improvement carried out on the premise of departing from the principle of the invention, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of rubidium and/or caesium cation in sodium-ion battery field as sodium-ion battery electrolysis additive application,
Wherein, described sodium-ion battery electrolyte includes described rubidium and/or caesium cation, electrolyte sodium salt and organic solvent；
Molar concentration of the described rubidium and/or caesium cation in described sodium-ion battery electrolyte is 0.01-0.2mol/L；It is described
Molar concentration of the electrolyte sodium salt in described sodium-ion battery electrolyte be 0.5-2mol/L.
2. application as claimed in claim 1, it is characterised in that
In described application, described rubidium and/or caesium cation is the SEI film forming addition as sodium-ion battery electrolyte
Agent；
And/or, the molar concentration of described rubidium and/or caesium cation in described sodium-ion battery electrolyte is 0.025-
0.1mol/L。
3. application as claimed in claim 1, it is characterised in that
In described sodium-ion battery electrolyte, described rubidium cation exists in the form of rubidium salt, and described rubidium salt is inorganic
Rubidium salt and/or organic rubidium salt；Described inorganic rubidium salt is preferably selected from RbPF6、RbClO4、RbNO3And Rb2CO3In one kind or many
Kind；Described organic rubidium salt is preferably selected from RbTFSI, RbCF3SO3、RbC2BF2O4、RbC4BO8And RbCH3SO3In one kind or many
Kind；Described rubidium salt is more preferably RbPF6And/or RbTFSI；
And/or, in described sodium-ion battery electrolyte, described caesium cation exists in the form of cesium salt, described cesium salt
For inorganic cesium salt and/or organic cesium salt；Described inorganic cesium salt is preferably selected from CsPF6、CsClO4、CsNO3And Cs2CO3In one
Plant or a variety of；Described organic cesium salt is preferably selected from CsTFSI, CsCF3SO3、CsC2BF2O4、CsC4BO8And CsCH3SO3In one
Plant or a variety of；Described cesium salt is more preferably CsPF6And/or CsTFSI.
4. application as claimed in claim 1, it is characterised in that
Molar concentration of the described electrolyte sodium salt in described sodium-ion battery electrolyte is 0.6-1.2mol/L, preferably
0.8-1.0mol/L；
And/or, described electrolyte sodium salt is selected from NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3、Na(CF3SO2)2N、NaBCl4、NaNO3、NaPOF4、NaSCN、NaCN、NaAsF6、NaTaF6、NaCF3CO2、NaSbF6、NaC6H5CO2、Na(CH3)
C6H4SO3、NaHSO4With NaB (C6H5)4In one or more, preferably NaPF6、NaClO4、NaSO3CF3With Na (CH3)C6H4SO3
In one or more, further preferred NaClO4And/or NaPF6。
5. application as claimed in claim 1, it is characterised in that
Organic solvent in described sodium-ion battery electrolyte includes carbonic ester, and described carbonic ester is preferably cyclic carbonate
And/or linear carbonate；Wherein, described cyclic carbonate is preferably selected from the one or more in PC, EC and BC；Described chain
Shape carbonic ester is preferably selected from the one or more in DMC, DEC, EMC, MPC, MF, EF, MA, EA and EP；When described organic molten
When agent also includes other solvents, other described solvents are preferably selected from the one or more in THF, DOL, DG, AN and DMSO.
6. the application as described in any one of Claims 1 to 5, it is characterised in that
Described sodium-ion battery electrolyte also includes removing described rubidium and/or caesium cation or described rubidium salt and/or cesium salt
Other sodium-ion battery electrolysis additives in addition；
Wherein, other described sodium-ion battery electrolysis additives include SEI cathode film formations additive, additives for overcharge protection addition
Agent, the additive of control electrolyte reclaimed water and HF contents, the additive for improving high temperature performance, flame-retardant additive, conductive addition
One or more in agent and multifunction additive；Preferably SEI cathode film formations additive, more preferably fluorinated SEI
Cathode film formation additive, one kind in FEC, EPFP, DFEC and TFP of described fluorinated SEI cathode film formation additives or
It is a variety of；
Wherein, the percentage composition of other described sodium-ion battery electrolysis additives be preferably 0.5%-8%, 1%-6% or
2%-5%；Described percentage composition refer to the quality of other described sodium-ion battery electrolysis additives described sodium from
Percentage in sub- battery electrolyte gross mass.
7. a kind of sodium-ion battery electrolyte, it includes rubidium and/or caesium cation, electrolyte sodium salt, and organic solvent, optional
Ground also includes other sodium-ion battery electrolysis additives；Wherein, described rubidium and/or caesium cation, described electrolyte sodium
Salt, described organic solvent, other described sodium-ion battery electrolysis additives are as described in any one of claim 1~6.
8. a kind of sodium-ion battery electrolysis additive, it includes rubidium and/or caesium cation or rubidium salt and/or cesium salt, alternatively
Also include other sodium-ion battery electrolysis additives；Wherein, described rubidium and/or caesium the cation such as institute of claim 1 or 2
State；Described rubidium salt and/or cesium salt are as claimed in claim 3；Other described sodium-ion battery electrolysis additive such as rights
It is required that described in 6.
9. sodium-ion battery electrolysis additive as claimed in claim 8, it is characterised in that described sodium-ion battery electrolysis
Solution additive is made up of described rubidium salt and/or cesium salt and at least one other described sodium-ion battery electrolysis additives；
Wherein, other described sodium-ion battery electrolysis additives are preferably fluorinated SEI cathode film formation additives, further preferably
For FEC and/or EPFP.
10. a kind of sodium-ion battery, it is characterised in that the electrolyte of described sodium-ion battery is as claimed in claim 6.
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| CN116565364A (en) * | 2023-07-10 | 2023-08-08 | 宁德时代新能源科技股份有限公司 | Battery monomer, positive pole piece, negative pole piece, isolation film, battery and electric equipment |
| CN116565364B (en) * | 2023-07-10 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Battery monomer, positive pole piece, negative pole piece, isolation film, battery and electric equipment |
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