CN106920988B - A kind of sodium-ion battery electrolyte, preparation method and application - Google Patents
A kind of sodium-ion battery electrolyte, preparation method and application Download PDFInfo
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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
- H01M10/054—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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of sodium-ion battery electrolyte, preparation method and its applications.Sodium-ion battery electrolyte of the invention includes sodium salt, non-aqueous organic solvent and additive；Wherein, the additive is sulfuric acid ester compound shown in formula I, the sultones class compound as shown in Formula II and fluorinated ethylene carbonate (FEC)；The non-aqueous organic solvent is carbonic ester or carbonic ester and carboxylate；The carbonic ester is cyclic carbonate and/or linear carbonate.Sodium-ion battery electrolyte of the invention is for the first time using cyclic sulfates class compound as additive application in sodium-ion battery field；There is excellent high-temperature storage performance, high temperature cyclic performance and low temperature discharge high rate performance with the sodium-ion battery that sodium-ion battery electrolyte of the invention is prepared.
Description
Technical field
The present invention relates to a kind of sodium-ion battery electrolyte, preparation method and applications.
Background technique
In recent years, as electronic equipment, electric tool, small power electric electrical automobile etc. are grown rapidly, high energy efficiency, resource are studied
Abundant and environmental-friendly energy storage material is the necessary condition that human society realizes sustainable development.It is in large scale to meet
The market demand, it is far from being enough for only relying on the performance measures battery material such as energy density, charge-discharge magnification.The manufacture of battery at
Whether this pollutes the environment with energy consumption and the recovery utilization rate of resource will also become the important indicator of evaluation battery material.
Sodium is one of more rich element of reserves on the earth, similar with the chemical property of lithium, therefore is equally applicable to lithium-ion electric pond body
System.Sodium-ion battery has many advantages compared to lithium ion battery, and such as at low cost, safety is good, with going deep into for research, sodium ion
Battery will increasingly have cost-effectiveness, and be expected to be widely used in future substitution lithium ion battery, and sodium-ion battery
As novel energy-storage battery, need to meet the performance requirement under different temperatures and high circulation requirement.
Chinese patent application CN 201510060712.7 discloses a kind of lithium-ion battery electrolytes and lithium ion secondary electricity
Pond can be restored on the cathode of lithium ion battery using it by adding a certain amount of silanes sulfuric ester and form Bao Erzhi
Close SEI film (solid electrolyte interface film), the cryogenic property and cycle performance of Lai Tigao battery.
It is used under wider temperature range and excellent cycle performance demand currently, exploitation can satisfy sodium-ion battery
Electrolyte it is particularly important.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome to be badly in need of exploitation in the prior art with excellent cryogenic property
The problem of with the sodium-ion battery of cycle performance, thus provide a kind of sodium-ion battery electrolyte, preparation method and its answer
With cyclic sulfates class compound as additive and is applied to sodium ion electricity for the first time by sodium-ion battery electrolyte of the invention
Pond field；The sodium-ion battery being prepared with sodium-ion battery electrolyte of the invention have excellent high-temperature storage performance,
High temperature cyclic performance and low temperature discharge high rate performance.
Although sodium-ion battery is similar with the basic principle of lithium ion battery, the half-cell prtential of sodium ion compares lithium ion
The high 0.3V of half-cell prtential, and sodium ion radius is far longer than lithium ion radius, so there is apparent in practical applications
Difference.The additive being applicable in lithium ion battery is not necessarily applied to sodium-ion battery, such as additive vinylene carbonate
(VC) it can increase the cyclical stability of lithium ion battery, but run counter to desire in sodium-ion battery.The present inventor couple
In how designing sodium-ion battery electrolyte to improve or improve the performance of sodium-ion battery and carry out repeatedly and in-depth study,
And obtain following achievements.
The present invention solves above-mentioned technical problem by following technical proposals.
The present invention provides a kind of sodium-ion battery electrolyte, and it includes sodium salt, non-aqueous organic solvent and additives；Its
In, the additive is sulfuric acid ester compound shown in formula I, sultones class compound and fluorine as shown in Formula II
For ethylene carbonate (FEC)；
In the present invention, the sulfuric acid ester compound shown in formula I is in the sodium-ion battery electrolyte
Mass percentage is 0.5%-5%, preferably 1%-3%, further preferred 2%.
In the sulfuric acid ester compound shown in formula I, R1For H or C1-C3Alkyl.Wherein, the C1-C3Hydrocarbon
Base is preferably C1-C3Alkyl, further preferably methyl or propyl；n1It is 1,2 or 3, preferably 1 or 2.
In the present invention, the sulfuric acid ester compound preferably sulfuric acid vinyl acetate (DTD, I-1) shown in formula I, 4- first
Base ethyl sulfate (I-2), 4- propyl ethyl sulfate (I-3), sulfuric acid acrylic ester (I-4), 4- methylsulfuric acid Asia propyl ester (I-5)
With one of 4- propyl sulfuric acid Asia propyl ester (I-6) or a variety of, further preferred sulfuric acid vinyl ester (DTD, I-1), 4- methyl sulphur
One of sour ethyl (I-2), sulfuric acid acrylic ester (I-4) and 4- methylsulfuric acid Asia propyl ester (I-5) are a variety of, further excellent
Select sulfuric acid vinyl ester (DTD, I-1).
In the present invention, matter of the sultones class compound as shown in Formula II in the sodium ion electrolyte
Amount percentage composition is 0.5%-6%, preferably 1%-5%, further preferred 3%.
In the sultones class compound as shown in Formula II, R2And R3It is each independently selected from H or C1-C6Hydrocarbon
Base, wherein the C1-C6Alkyl is preferably C1-C3Alkyl, further preferably C1-C3Alkyl, still more preferably methyl or
Ethyl；n2It is 1,2 or 3, preferably 1 or 2.
In the present invention, the preferred 1- propenyl-1,3-sulfonic acid lactone of sultones class compound as shown in Formula II
(PST, II-1), 1- acrylic -1- methyl-1, in 3- sultones (II-2), 1- acrylic -1,2- dimethyl -1,3- sulfonic acid
Ester (II-3), 1- acrylic -1- ethyl -1,3- sultones (II-4), 1- acrylic -1,2- diethyl -1,3- sultones
(II-5), 1- cyclobutenyl -1,4- sultones (II-6), 1- cyclobutenyl -1- methyl-1,4- sultones (II-7), 1- butylene
Base -1,2- dimethyl -1,4- sultones (II-8), 1- cyclobutenyl -1- ethyl -1,4- sultones (II-9) and 1- butylene
One of base -1,2- diethyl-Isosorbide-5-Nitrae-sultones (II-10) is a variety of, in further preferred 1- acrylic -1,3- sulfonic acid
Ester (PST, II-1), 1- acrylic -1- methyl-1,3- sultones (II-2), 1- cyclobutenyl-Isosorbide-5-Nitrae-sultones (II-6) and
1- cyclobutenyl -1- methyl-1, one of 4- sultones (II-7) or a variety of, still more preferably 1- acrylic -1,3- sulphur
Acid lactone (PST, II-1).
In the present invention, quality percentage of the fluorinated ethylene carbonate (FEC) in the sodium ion electrolyte contains
Amount is 1%-6%, preferably 2%-4%, further preferably 3%.
In the present invention, mass percentage of the additive in the sodium ion electrolyte is preferably 2%-
17%, further preferably 5%-7%, still more preferably 6%.
In the present invention, the additive preferably by fluorinated ethylene carbonate (FEC), sulfuric acid vinyl ester (DTD, I-1) and
1- propenyl-1,3-sulfonic acid lactone (PST, II-1) composition.
In the present invention, the sodium salt is sodium salt used in sodium-ion battery electrolyte routine in this field, and the present invention is excellent
Select NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3、NaBCl4、NaNO3、NaPOF4、NaSCN、NaCN、NaAsF6、
NaCF3CO2、NaSbF6、NaC6H5CO2、Na(CH3)C6H4SO3、NaHSO4With NaB (C6H5)4One of or it is a variety of, further it is excellent
Select NaPF6、NaClO4、NaSO3CF3With Na (CH3)C6H4SO3One of or a variety of, still more preferably NaClO4。
In the present invention, the concentration of the sodium salt can be dense for the routine of sodium salt in sodium-ion battery electrolyte in this field
Degree, the present invention is preferably 0.5-2.0M, further preferably 0.8-1.2M, such as 1M.
In the present invention, the non-aqueous organic solvent is carbonic ester or carbonic ester and carboxylate, and the carbonic ester is ring
Shape carbonic ester and/or linear carbonate.
It is described when the carbonic ester is cyclic carbonate or cyclic carbonate and linear carbonate in the present invention
Cyclic carbonate is preferably propene carbonate (PC) and/or ethylene carbonate (EC)；The cyclic carbonate is described non-
Volumn concentration preferred 35%-65%, further preferred 40%-60% in aqueous organic solvent.
It is described when the carbonic ester is linear carbonate or cyclic carbonate and linear carbonate in the present invention
Linear carbonate is preferably one of dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) or more
Kind；Volumn concentration of the linear carbonate in the non-aqueous organic solvent is preferably 40%-60%.
In the present invention, when the carbonic ester be cyclic carbonate and linear carbonate when, the cyclic carbonate and
The volume ratio of linear carbonate is preferably 2:3-3:2.
In the present invention, when the non-aqueous organic solvent is carbonic ester and carboxylate, the carboxylate is preferably first
One of sour methyl esters (FA), ethyl acetate (EA) and methyl butyrate (BA) are a variety of；Further preferably ethyl acetate (EA).
In the present invention, when the non-aqueous organic solvent is carbonic ester and carboxylate, the carboxylate is described
Volumn concentration in non-aqueous organic solvent preferably≤70%, further preferably≤50%.
In the present invention, when the non-aqueous organic solvent is carbonic ester and carboxylate, the carbonic ester and described
The percent by volume of carboxylate is preferably 3:7-7:3.
In the present invention, the non-aqueous organic solvent is preferably made of propene carbonate (PC) and methyl ethyl carbonate (EMC),
Further preferably the two volume ratio is 2:3-3:2, such as 1:1.
In the present invention, the non-aqueous organic solvent is preferably made of ethylene carbonate (EC) and methyl ethyl carbonate (EMC),
Further preferably the two volume ratio is 2:3-3:2, such as 1:1.
In the present invention, the non-aqueous organic solvent is preferably made of propene carbonate (PC) and dimethyl carbonate (DMC),
Further preferably the two volume ratio is 2:3-3:2, such as 1:1.
In the present invention, the non-aqueous organic solvent is preferably made of propene carbonate (PC) and ethyl acetate (EA), into
The preferred the two volume ratio of one step is 2:3-3:2, such as 1:1.
The present invention also provides a kind of preparation method of sodium-ion battery electrolyte, electrolyte in this field is used to prepare
Conventional method carry out.Preferably it includes following steps by the present invention: being added such as in non-aqueous organic solvent as described above
The sodium salt and additive as described above, be uniformly mixed,.
The present invention still further provides application of the sodium-ion battery electrolyte in sodium-ion battery described in one kind.
The present invention still further provides a kind of sodium-ion battery comprising positive plate, negative electrode tab, isolation film, electrolyte；
Wherein, the positive plate includes plus plate current-collecting body and the anode containing positive electrode active materials that is set on plus plate current-collecting body
Diaphragm；The negative electrode tab includes negative current collector and the cathode containing negative electrode active material that is set on negative current collector
Diaphragm；The isolation film is interval between positive plate and negative electrode tab；The electrolyte is sodium-ion battery as described above
Electrolyte.
In the present invention, the positive electrode active materials are in this field used in sodium-ion battery routine, including can deviate from, connect
By the material of sodium ion；The present invention is preferably sodium compound transition metal oxide.Wherein, the sodium transition metal combined oxidation
Object is preferably that sodium transition metal oxide, sodium transition metal oxide add the change that other transition metal or nontransition metal obtain
Close one of object or a variety of, further preferred sodium cobalt/cobalt oxide, sodium manganese oxide, sodium Quito element/transition metal compound, mistake
Cross one of metal tripolyphosphate sodium salt and transition metal fluorophosphoric acid sodium salt or a variety of；It is still more preferably NaxCoO2、
NaxMnO2、NaNi0.33Fe0.33Mn0.33O2、NaFePO4、NaCoPO4、NaVPO4One of or it is a variety of.
In the present invention, the negative electrode active material is in this field used in sodium-ion battery routine, including can receive, take off
The material of sodium ion out.The present invention is preferably soft carbon, hard carbon, acetylene black, sodium titanate and can be formed in the metal of alloy with sodium
It is one or more.
Sodium-ion battery of the invention further may also include battery outer packing.
The present invention still further provides the preparation method of sodium-ion battery described in one kind, use in this field sodium from
The conventional method of sub- battery preparation carries out.Preferably it includes following steps by the present invention: by positive plate, isolation film, negative electrode tab
It folds in order, makes that isolation film is in positive plate and buffer action is played in the centre of negative electrode tab, stacking obtains naked battery core later, will
Naked battery core is placed in outer packing, is injected sodium-ion battery electrolyte as described above and is encapsulated, is melted into.
Unless otherwise instructed, non-described in volumn concentration=100%* of each component in the non-aqueous organic solvent
The total volume of the non-aqueous organic solvent of the volume of each component in aqueous organic solvent/described；The matter of each component in the additive
Measure the gross mass of the sodium-ion battery electrolyte of the quality of each component in additive described in percentage composition=100%*/described.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
1, the present invention is for the first time using sulfuric acid ester compound shown in formula I as electrolysis additive, and is applied successfully
In sodium-ion battery, high temperature storage, cycle performance and the cryogenic property of sodium-ion battery are improved.
2, the present invention has found sulfuric acid ester compound and the sulfonic acid as shown in Formula II shown in formula I by further investigation
Lactone compound can form stable cathode SEI protective film, portion with fluorinated ethylene carbonate (FEC) in negative terminal surface jointly
Divide and fluorinated ethylene carbonate (FEC) is prevented to restore to form HF gas in negative terminal surface, to avoid negative electrode active material by HF
The corrosion of gas；And the sultones class compound as shown in Formula II can be in positive table while cathode forms stable protective film
Face forms stable SEI film, and the dissolution particular for manganese is helpful, and sodium ion electricity is realized under the synergistic effect of above-mentioned three
The high-temperature storage performance in pond and the raising of high temperature cyclic performance.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, unless otherwise instructed, content is mass percentage.
Embodiment 1-12 and comparative example 1-10:
By taking embodiment 3 as an example, the preparation process of sodium-ion battery electrolyte is as follows: the electrolyte of sodium-ion battery with
The NaClO of 1mol/L4It is non-with the mixture (volume ratio 1:1) of propene carbonate (PC) and methyl ethyl carbonate (EMC) for sodium salt
Aqueous organic solvent, additive is by fluorinated ethylene carbonate (FEC), cyclic sulfates and unsaturated sulfonic acid lactone compound group
At wherein cyclic sulfates are sulfuric acid vinyl ester (DTD), unsaturated sulfonic acid lactone is 1- propenyl-1,3-sulfonic acid lactone
(PST)。
Wherein, the specific addition manner of sodium-ion battery electrolyte is as shown in table 1 in each embodiment and comparative example.
1 sodium-ion battery electrolyte addition manner of table
The preparation of sodium-ion battery positive plate: by positive electrode active materials NaNi1/3Fe1/3Mn1/3O2, it is conductive agent acetylene black, viscous
Knot agent polyvinylidene fluoride (PVDF) is mixed by weight 97:1.5:1.5, and N-Methyl pyrrolidone (NMP) solvent is added,
It is thoroughly mixed uniformly, obtains anode sizing agent.Anode sizing agent is coated on collector Al foil, by drying, cold pressing, cutting
And soldering polar ear, obtain the positive plate of sodium-ion battery.
The preparation of sodium-ion battery negative electrode tab: negative electrode active material graphite, conductive agent acetylene black, binder are gathered into inclined difluoro
Ethylene (PVDF) is mixed by weight 94:3:3, and N-Methyl pyrrolidone (NMP) solvent is added, and is thoroughly mixed
It is even, obtain negative electrode slurry.Negative electrode slurry is coated on collector Al foil, by drying, cold pressing, cutting and soldering polar ear,
Obtain the negative electrode tab of sodium-ion battery.
The preparation of sodium-ion battery: positive plate, isolation film, negative electrode tab are folded in order, and isolation film is made to be in positive plate
Buffer action is played with the centre of negative electrode tab, stacking obtains naked battery core later, and naked battery core is placed in outer packing, injects electrolyte
And encapsulate, be melted into, obtain sodium-ion battery.
Following effect example provides the sodium-ion battery of embodiment 1-12 and comparative example 1-10 and its performance of electrolyte
Test process and test result, concrete outcome is see table 2.
Effect example 1: the high-temperature storage performance test of sodium-ion battery
At 25 DEG C, 5 sodium-ion batteries are respectively taken, with 0.5C multiplying power constant current charging to 4.0V, then the perseverance at 4.0V
Constant-voltage charge is at 4.0V fully charged state, completely fills the thickness of sodium-ion battery before test storage and be denoted as to 0.05C
D0, sodium-ion battery will be completely filled later and is placed in 60 DEG C of baking ovens, is taken out after 7 days, the sodium-ion battery after test storage immediately
Thickness is simultaneously denoted as D1。
Thickness swelling ε=(D1-D0)/D0* 100%
With the average value of the thickness swelling after 5 sodium-ion battery high-temperature storage, stored up as the sodium-ion battery high temperature
Thickness swelling after depositing.
Effect example 2: the high temperature cyclic performance test of sodium-ion battery
At 45 DEG C, 5 sodium-ion batteries are respectively taken, 4.0V are charged to 1C multiplying power constant current, then constant-voltage charge to electric current is
0.05C, then with 1C multiplying power constant-current discharge to 2.0V, it is C that discharge capacity, which is denoted as capacity for the first time,1, repeat the process and carry out cyclicity
It can test, the capacity after record circulation 500 times is C500。
Capacity retention ratio (%)=C500/C1* 100%.
Capacity retention ratio with the average value of 5 sodium-ion battery capacity retention ratios, as the sodium-ion battery.
Effect example 3: the low temperature discharge high rate performance test of sodium-ion battery
At 25 DEG C, 5 sodium-ion batteries are respectively taken, with 0.5C multiplying power constant current charging to 4.0V, then it is constant with 4.0V
Voltage charges to 0.05C, stands 60min at 25 DEG C and -10 DEG C respectively later, then be discharged to electricity with 0.2C multiplying power constant current
Pressure is 3.0V.Record the discharge capacity D (25 DEG C) and D (- 10 DEG C) of sodium-ion battery at different temperatures.
The low temperature discharge capacity conservation rate of sodium-ion battery.
Low temperature discharge with the average value of 5 sodium-ion battery low temperature discharge capacity conservation rates, as the sodium-ion battery
Capacity retention ratio.
The performance test results of table 2 embodiment 1-12 and comparative example 1-10
Next the performance test results of sodium-ion battery of the invention are analyzed:
It can be seen that the electricity in the FEC for being 3% containing mass fraction from the test result of embodiment 1-5 and comparative example 7,8
The PST that addition mass fraction is 1% in liquid is solved, while the sulfuric acid ethylene that addition mass fraction is 0.5%-5% in the electrolytic solution
Ester (DTD), high-temperature storage performance, cycle performance and -10 DEG C of discharge performances of sodium-ion battery have obvious improvement, sulfuric acid second
The additive amount of enester (DTD) is preferably 1%-3%.Sulfuric acid vinyl ester (DTD) can also be in solvent ethylene carbonate (EC) negative
Low-impedance cathode SEI protective film is formed in negative terminal surface before pole surface is decomposed, therefore the impedance of sodium-ion battery obtains
It is apparent to reduce, so that the low temperature discharge high rate performance of sodium-ion battery is improved.The additive amount mistake of sulfuric acid vinyl ester (DTD)
The high or too low effect that the high-temperature storage performance of sodium-ion battery, cycle performance and -10 DEG C of discharge performances cannot be played with improvement.
This is because when sulfuric acid vinyl ester (DTD) content is less, with fluorinated ethylene carbonate (FEC) and 1- acrylic -1,3- sulfonic acid
The SEI film that lactone (PST) generates is unstable, and when sulfuric acid vinyl ester (DTD) content is higher, although can obviously inhibit HF gas
Body, since the positive SEI protective film of generation is blocked up overstocked, hinders sodium ion to the corrosivenesses of positive electrode active materials
Normal deintercalation process, therefore the capacity of sodium-ion battery can be played and be had adverse effect on, but also can seriously affect sodium from
The low temperature discharge high rate performance of sub- battery.
It can be seen that from the test result of embodiment 2,6-9 and comparative example 5,6 in the fluoro for being 3% containing mass fraction
The sulfuric acid vinyl ester (DTD) of addition 1% in the electrolyte of ethylene carbonate (FEC), while adding the 1- propylene of 0.5%-6%
Base -1,3- sultones (PST) improves high-temperature storage performance, cycle performance and -10 DEG C of electric discharges of sodium-ion battery well
Performance.With the increase of 1- propenyl-1,3-sulfonic acid lactone (PST) content, the SEI film that positive and negative anodes are formed is gradually stable, works as 1-
When the content of propenyl-1,3-sulfonic acid lactone (PST) is greater than 1%, sodium-ion battery shows optimal high-temperature storage performance, follows
Ring performance and -10 DEG C of discharge performances, continue to add 1- propenyl-1,3-sulfonic acid lactone (PST) to 6%, the 1- propylene of high-content
The SEI film that base -1,3- sultones (PST) generates is thicker, and impedance is larger, and the chemical property of sodium-ion battery fails to improve.
The additive amount of 1- acrylic -1,3- sultones (PST) is preferably 1%-5%.
It can be seen that from the test result of comparative example 4 and do not add fluorinated ethylene carbonate (FEC), sodium ion in electrolyte
The high-temperature storage performance of battery, cycle performance and -10 DEG C of discharge performances are poor, because not adding fluorinated ethylene carbonate
(FEC) the SEI film that electrolyte generates is unstable, and SEI film is destroyed during charge and discharge, causes battery bulging, capacity
Decline, seriously affects the chemical property of sodium-ion battery.
It can be seen that the electrolyte in the fluorinated ethylene carbonate (FEC) containing 3% from the test result of comparative example 1-3
Middle 1% sulfuric acid vinyl ester (DTD) that adds respectively is compared with only addition 1%1- propenyl-1,3-sulfonic acid lactone (PST), sulfuric acid second
Enester (DTD) is preferable to the high-temperature storage performance of sodium-ion battery, cycle performance and -10 DEG C of discharge performance effects.
If the volume that can be seen that linear carbonate from the test result of comparative example 9-10 is greater than non-aqueous organic solvent
The 65% of total volume can improve the risk that high temperature produces gas although then helpful to the conductivity of electrolyte；If chain carbon
The volume of acid esters is less than the 35% of the total volume of non-aqueous organic solvent, then has negative impact to low-temperature conductivity, and then influence
The low temperature discharge high rate performance of sodium-ion battery.
Claims (20)
1. a kind of sodium-ion battery electrolyte, it includes sodium salt, non-aqueous organic solvent and additives；Wherein, the additive
For sulfuric acid ester compound shown in formula I, sultones class compound and fluorinated ethylene carbonate as shown in Formula II；
Wherein, quality percentage of the sulfuric acid ester compound shown in formula I in the sodium-ion battery electrolyte
Content is 0.5%-5%；In the sulfuric acid ester compound shown in formula I, R1For H or C1-C3Alkyl, n1For 1,2 or
3；Mass percentage of the sultones class compound as shown in Formula II in the sodium ion electrolyte be
0.5%-6%；In the sultones class compound as shown in Formula II, R2And R3It is each independently selected from H or C1-C6Hydrocarbon
Base, n2It is 1,2 or 3；Mass percentage of the fluorinated ethylene carbonate in the sodium ion electrolyte is 1%-
6%；The non-aqueous organic solvent is carbonic ester or carbonic ester and carboxylate, the carbonic ester be cyclic carbonate and/or
Linear carbonate；When the carbonic ester is linear carbonate or cyclic carbonate and linear carbonate, the chain carbon
Volumn concentration of the acid esters in the non-aqueous organic solvent is 35%-65%.
2. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
Mass percentage of the sulfuric acid ester compound shown in formula I in the sodium-ion battery electrolyte be
1%-3%；
And/or in the sulfuric acid ester compound shown in formula I, the C1-C3Alkyl is C1-C3Alkyl；n1For 1 or
2；
And/or quality percentage of the sultones class compound as shown in Formula II in the sodium ion electrolyte
Content is 1%-5%；
And/or in the sultones class compound as shown in Formula II, the C1-C6Alkyl is C1-C3Alkyl；n2It is 1
Or 2；
And/or mass percentage of the fluorinated ethylene carbonate in the sodium ion electrolyte is 2%-4%；
And/or mass percentage of the additive in the sodium ion electrolyte is 2%-17%.
3. sodium-ion battery electrolyte as claimed in claim 2, which is characterized in that wherein,
Mass percentage of the sulfuric acid ester compound shown in formula I in the sodium-ion battery electrolyte be
2%；
And/or in the sulfuric acid ester compound shown in formula I, the C1-C3Alkyl is methyl or propyl；n1For 1 or
2；
And/or quality percentage of the sultones class compound as shown in Formula II in the sodium ion electrolyte
Content is 3%；
And/or in the sultones class compound as shown in Formula II, the C1-C3Alkyl is C1-C3Alkyl；n2For 1 or
2；
And/or mass percentage of the fluorinated ethylene carbonate in the sodium ion electrolyte is 3%；
And/or mass percentage of the additive in the sodium ion electrolyte is 5%-7%.
4. sodium-ion battery electrolyte as claimed in claim 3, which is characterized in that wherein,
In the sultones class compound as shown in Formula II, the C1-C3Alkyl is methyl or ethyl；n2It is 1 or 2；
And/or mass percentage of the additive in the sodium ion electrolyte is 6%.
5. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
The sulfuric acid ester compound shown in formula I is sulfuric acid vinyl ester, 4- methyl ethyl sulfate, 4- propyl sulfuric acid Asia
One of ethyl ester, sulfuric acid acrylic ester, 4- methylsulfuric acid Asia propyl ester and 4- propyl sulfuric acid Asia propyl ester are a variety of；
And/or the sultones class compound as shown in Formula II is 1- propenyl-1,3-sulfonic acid lactone, 1- acrylic-
1- methyl-1,3- sultones, 1- acrylic -1,2- dimethyl -1,3- sultones, 1- acrylic -1- ethyl -1,3- sulfonic acid
Lactone, 1- acrylic -1,2- diethyl -1,3- sultones, 1- cyclobutenyl-Isosorbide-5-Nitrae-sultones, 1- cyclobutenyl -1- methyl -
1,4- sultones, 1- cyclobutenyl -1,2- dimethyl -1,4- sultones, 1- cyclobutenyl -1- ethyl -1,4- sultones and
One of 1- cyclobutenyl -1,2- diethyl -1,4- sultones is a variety of；
And/or the sodium salt is NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3、NaBCl4、NaNO3、NaPOF4、
NaSCN、NaCN、NaAsF6、NaCF3CO2、NaSbF6、NaC6H5CO2、Na(CH3)C6H4SO3、NaHSO4With NaB (C6H5)4In
It is one or more；
And/or the concentration of the sodium salt is 0.5-2.0M.
6. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
The sulfuric acid ester compound shown in formula I be sulfuric acid vinyl ester, 4- methyl ethyl sulfate, sulfuric acid acrylic ester and
One of 4- methylsulfuric acid Asia propyl ester is a variety of；
And/or the sultones class compound as shown in Formula II is 1- propenyl-1,3-sulfonic acid lactone, 1- acrylic-
1- methyl-1,3- sultones, 1- cyclobutenyl -1,4- sultones and 1- cyclobutenyl -1- methyl-1, one in 4- sultones
Kind is a variety of；
And/or the sodium salt is NaPF6、NaClO4、NaSO3CF3With Na (CH3)C6H4SO3One of or it is a variety of；
And/or the concentration of the sodium salt is 0.8-1.2M.
7. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
The sulfuric acid ester compound shown in formula I is sulfuric acid vinyl ester；
And/or the sultones class compound as shown in Formula II is 1- propenyl-1,3-sulfonic acid lactone；
And/or the sodium salt is NaClO4；
And/or the concentration of the sodium salt is 1M.
8. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
When the carbonic ester is cyclic carbonate or cyclic carbonate and linear carbonate, the cyclic carbonate is
Propene carbonate and/or ethylene carbonate；Volume basis of the cyclic carbonate in the non-aqueous organic solvent contains
Amount is 35%-65%；
When the carbonic ester is linear carbonate or cyclic carbonate and linear carbonate, the linear carbonate is
One of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate are a variety of；The linear carbonate is described non-aqueous
Volumn concentration in organic solvent is 40%-60%；
When the carbonic ester is cyclic carbonate and linear carbonate, the body of the cyclic carbonate and linear carbonate
Product is than being 2:3-3:2.
9. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
When the carbonic ester is cyclic carbonate or cyclic carbonate and linear carbonate, the cyclic carbonate exists
Volumn concentration in the non-aqueous organic solvent is 40%-60%.
10. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein, when the non-aqueous organic solvent
When for carbonic ester and carboxylate, the carboxylate is one of methyl formate, ethyl acetate and methyl butyrate or a variety of；Institute
Volumn concentration of the carboxylate stated in the non-aqueous organic solvent is≤70%；
And/or the percent by volume of the carbonic ester and the carboxylate is 3:7~7:3.
11. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein, when the non-aqueous organic solvent
When for carbonic ester and carboxylate, the carboxylate is ethyl acetate；The carboxylate is in the non-aqueous organic solvent
Volumn concentration be≤50%.
12. sodium-ion battery electrolyte as described in claim 1, which is characterized in that wherein,
The additive is made of fluorinated ethylene carbonate, sulfuric acid vinyl ester and 1- acrylic -1,3- sultones；
And/or the non-aqueous organic solvent is made of propene carbonate and methyl ethyl carbonate, the two volume ratio is 2:3-3:2；
Or, the non-aqueous organic solvent is made of ethylene carbonate and methyl ethyl carbonate, the two volume ratio is 2:3-3:2；
Or, the non-aqueous organic solvent is made of propene carbonate and dimethyl carbonate, the two volume ratio is 2:3-3:2；
Or, the non-aqueous organic solvent is made of propene carbonate and ethyl acetate, the two volume ratio is 3:7-7:3.
13. a kind of preparation method of such as described in any item sodium-ion battery electrolyte of claim 1-12, it includes following steps
It is rapid: be added in the non-aqueous organic solvent sodium salt and the additive, be uniformly mixed,.
14. a kind of such as described in any item sodium-ion battery electrolyte of claim 1-12 are as electrolyte in sodium-ion battery
Application.
15. a kind of sodium-ion battery comprising positive plate, negative electrode tab, isolation film, electrolyte；The positive plate includes anode
Collector and the positive diaphragm containing positive electrode active materials being set on plus plate current-collecting body；The negative electrode tab includes cathode
Collector and the cathode membrane containing negative electrode active material being set on negative current collector；The isolation film is interval in just
Between pole piece and negative electrode tab；It is characterized in that, the electrolyte is such as the described in any item sodium ion electricity of claim 1-12
Pond electrolyte；
Wherein, the positive electrode active materials include the material that can deviate from, receive sodium ion；
Wherein, the negative electrode active material includes the material that can receive, deviate from sodium ion.
16. sodium-ion battery as claimed in claim 15, which is characterized in that the positive electrode active materials are multiple for sodium transition metal
Close oxide；The negative electrode active material is soft carbon, hard carbon, acetylene black, sodium titanate and the metal that alloy can be formed with sodium
One of or it is a variety of.
17. sodium-ion battery as claimed in claim 15, which is characterized in that the positive electrode active materials are sodium oxo transition metal
Compound, sodium transition metal oxide add one of compound that other transition metal or nontransition metal obtain or a variety of.
18. sodium-ion battery as claimed in claim 15, which is characterized in that the positive electrode active materials be sodium cobalt/cobalt oxide,
In sodium manganese oxide, sodium Quito element/transition metal compound, transition metal phosphate sodium salt and transition metal fluorophosphoric acid sodium salt
It is one or more.
19. sodium-ion battery as claimed in claim 15, which is characterized in that the positive electrode active materials are NaxCoO2、
NaxMnO2、NaNi0.33Fe0.33Mn0.33O2、NaFePO4、NaCoPO4、NaVPO4One of or it is a variety of.
20. a kind of preparation method of such as described in any item sodium-ion batteries of claim 15-19, it includes following steps: will
The positive plate, the isolation film, the negative electrode tab are folded in order, and the isolation film is made to be in the anode
Buffer action is played in the centre of piece and the negative electrode tab, and stacking obtains naked battery core later, and naked battery core is placed in outer packing, infuses
Enter such as the described in any item sodium-ion battery electrolyte of claim 1-12 and encapsulates, is melted into.
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| CN109309247A (en) * | 2017-07-27 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical energy storage device |
| CN107565158B (en) * | 2017-08-29 | 2020-01-14 | 深圳中科瑞能实业有限公司 | Electrolyte for sodium ion battery, preparation method and sodium ion battery containing electrolyte for sodium ion battery |
| JP2019046614A (en) * | 2017-08-31 | 2019-03-22 | 三菱ケミカル株式会社 | Non-aqueous electrolyte solution for sodium ion secondary battery and sodium ion secondary battery |
| CN109786827A (en) * | 2018-02-12 | 2019-05-21 | 上海紫剑化工科技有限公司 | A kind of sodium-ion battery electrolyte, its additive, preparation method and application |
| CN109103498B (en) * | 2018-08-27 | 2020-12-18 | 中国电子新能源（武汉）研究院有限责任公司 | Sodium ion battery electrolyte and preparation method and application thereof |
| CN110518287B (en) * | 2019-07-03 | 2022-02-11 | 上海紫剑化工科技有限公司 | Sodium ion electrolyte, secondary battery, preparation method and application |
| JPWO2020175638A1 (en) * | 2019-02-28 | 2021-12-23 | 三菱ケミカル株式会社 | Non-aqueous electrolyte solution for sodium ion secondary battery and sodium ion secondary battery |
| CN113130971A (en) * | 2019-12-31 | 2021-07-16 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN113871714A (en) * | 2020-06-30 | 2021-12-31 | 张家港市国泰华荣化工新材料有限公司 | Electrolyte of sodium ion battery and application |
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| CN114006042A (en) * | 2021-10-21 | 2022-02-01 | 湖南立方新能源科技有限责任公司 | Electrolyte for sodium ion battery and sodium ion battery |
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| CN114069051A (en) * | 2021-11-23 | 2022-02-18 | 天津中电新能源研究院有限公司 | Fluoro-carboxylic acid ester based low-temperature electrolyte and sodium ion battery containing same |
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| CN114156539A (en) * | 2021-12-21 | 2022-03-08 | 华南师范大学 | Sodium secondary battery electrolyte and sodium secondary battery |
| CN114361592B (en) * | 2021-12-28 | 2023-08-01 | 大连中比动力电池有限公司 | Additive and application thereof in sodium ion battery electrolyte |
| CN114400382A (en) * | 2022-01-10 | 2022-04-26 | 温州大学碳中和技术创新研究院 | Sodium metal battery high-voltage electrolyte matched with cobalt-based phosphate positive electrode material |
| CN114497744A (en) * | 2022-03-07 | 2022-05-13 | 天津市捷威动力工业有限公司 | Sodium ion electrolyte and application thereof, sodium ion battery and preparation method thereof |
| CN114695974B (en) * | 2022-04-21 | 2024-08-16 | 南开大学 | Low-temperature water-based ion battery electrolyte and application thereof in water-based ion battery |
| CN116885278A (en) * | 2023-07-26 | 2023-10-13 | 华南师范大学 | Electrolyte and sodium ion battery |
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