CN108808094A - Ultralow temperature electrolyte and preparation method thereof and the battery and preparation method thereof for using the ultralow temperature electrolyte - Google Patents
Ultralow temperature electrolyte and preparation method thereof and the battery and preparation method thereof for using the ultralow temperature electrolyte Download PDFInfo
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- CN108808094A CN108808094A CN201810546667.XA CN201810546667A CN108808094A CN 108808094 A CN108808094 A CN 108808094A CN 201810546667 A CN201810546667 A CN 201810546667A CN 108808094 A CN108808094 A CN 108808094A
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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
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- H01M10/0569—Liquid materials characterised by the solvents
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical fields of battery electrolyte, and in particular to ultralow temperature electrolyte and preparation method thereof and the battery and preparation method thereof using the ultralow temperature electrolyte；The technical issues of solution is：A kind of ultralow temperature electrolyte and preparation method thereof and the battery and preparation method thereof using the ultralow temperature electrolyte are provided, high rate charge-discharge can be carried out under ultra-low temperature surroundings；The technical solution used for：Ultralow temperature electrolyte, including：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；Wherein：The solvent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Aqueous solution；The electrolytic salt is：Solubility >=3Metal salt.
Description
Technical field
The invention belongs to the technical fields of battery electrolyte, and in particular to ultralow temperature electrolyte and preparation method thereof and make
With the battery and preparation method thereof of the ultralow temperature electrolyte.
Background technology
As fossil fuel excessively develops and uses caused energy crisis, each metal ion species secondary cell especially lithium
Ion secondary battery is increasingly becoming new energy field with advantages such as its high-energy density, flexibility, portability and service life length
The most energy storage technology of application prospect.
However, although lithium ion has been successfully applied to every field in life, at some with extremely low temperature
Environmental area, such as aerospace, the fields such as deep-sea exploration and south poles exploration, which exist, applies obstacle；Under low temperature, lithium-ion electric
The main reason for energy density and power density conservation rate in pond can all be greatly reduced, the phenomenon can be attributed to electrolyte conductance
The decline of rate, the increase of solid phase interface impedance between material and electrolyte, electrode material and electrolyte interface electric charge transfer are slack-off,
And migration velocity of the lithium ion in electrode material is slack-off.
In certain temperature range, electrolyte is the most critical factor for determining these performances；Currently, improving lithium-ion electric
The method of pond cryogenic property mainly has the following：
One, the ionic conductivity under electrolyte low temperature is improved by the total addition of multi-solvents and adjusting proportioning；
Two, improve the solid electrolyte at interface by adding various additives（SEI）Film reduces SEI low thermal resistances；
Three, by coating or being modified the diffusion velocity for improving lithium ion in electrode material；
Above-mentioned preceding 2 points of modifications that can be attributed to electrolyte, current research can only very limited improvement battery in low temperature
The problem of lower internal resistance significantly increases, especially in high rate charge-discharge（1C）In the case of, the capacity retention ratio of battery is very low
Problem never significantly improves.
Invention content
The present invention overcomes the shortcomings of the prior art, technical problem to be solved to be：A kind of ultralow temperature electrolysis is provided
Liquid and preparation method thereof and the battery and preparation method thereof for using the ultralow temperature electrolyte can carry out big under ultra-low temperature surroundings
Rate charge-discharge.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
Ultralow temperature electrolyte, including：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolysis
Liquid；Wherein：The solvent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Single solvent, Huo Zheqi
Mixed solvent；The electrolytic salt is：Solubility >=3 in above-mentioned selected solventMetal salt.
Preferably, the solvent is：In water, dimethyl carbonate, ethylene carbonate, diethyl carbonate, acetonitrile, ethyl acetate
One or more kinds of combinations.
Preferably, the electrolytic salt is：Trifluoromethanesulfonic acid lithium（Chemical formula is：, it is abbreviated as：LiOTf））,
It is double（Fluorine sulphonyl）Imine lithium（Chemical formula is：, it is abbreviated as：LiFSI）, it is double（Fluoroform sulphonyl）Imine lithium（Change
Formula is：, be abbreviated as：LiTFSI）, it is double（Pentafluoroethyl group sulfonyl）Imino group lithium（Chemical formula is：, be abbreviated as：LiBETI）One or more of combination.
Correspondingly, ultralow temperature electrolyte and preparation method thereof, including step：By viscosity 0 ~ 2.0Between or dielectric
Constant >=30Aqueous solution, as solvent；To solubility >=3 in waterMetal salt, as electrolytic salt；
Electrolytic salt is added in a solvent；It stirs and is uniformly mixed, it is 3 ~ 25 to obtain mass concentrationElectrolyte.
Correspondingly, a kind of ultralow temperature lithium battery, including：Anode, cathode, diaphragm and the electrolysis being arranged in battery case
Liquid；The electrolyte is：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；It is described
Solvent be：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Aqueous solution；The electrolytic salt is：It is molten
Xie Du >=3Metal salt.
Preferably, the positive active material that the anode uses for：、 、、、AndIn one or several kinds of compounds combination；
The negative electrode active material that the cathode uses for：、、 、
In one or several kinds of compounds combination；
Wherein：In compound：M separate is Fe, Co, Ni, Mn, Mo, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti
In any one；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Correspondingly, a kind of preparation method of ultralow temperature lithium battery, including：Positive active material, first are added into solvent
Conductive material and first binder obtain the first electrode slurry, the first electrode slurry are coated uniformly on the first collection after mixing
On fluid, roll-in after drying obtains positive plate；Negative electrode active material is added into solvent, the second conductive material and second bonds
Agent obtains the second electrode slurry, the second electrode slurry is coated uniformly on the second collector after mixing, roll-in after drying,
Obtain negative plate；The positive plate, negative plate, diaphragm of preparation are assembled in battery case；Electrolyte is injected into battery case,
Obtain ultralow temperature battery；Wherein：The electrolyte is：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；The solvent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30It is water-soluble
Liquid；The electrolytic salt is：Solubility >=3Metal salt.
Preferably, the positive active material that the anode uses for：、、、、AndIn one or several kinds of compounds group
It closes；The negative electrode active material that the cathode uses for：、、 、In one or several kinds of compounds combination；
Wherein：In compound：M separate is Fe, Co, Ni, Mn, Mo, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti
In any one；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Preferably, the solvent is N-Methyl pyrrolidone；First conductive material used, the second conductive material are conduction
Carbon black；First binder used, the second binder are any one in Kynoar, polytetrafluoroethylene (PTFE).
Preferably, the positive active material, conductive black, binder mass ratio be 92:5:3.
The present invention has the advantages that compared with prior art：
The low-temperature electrolyte of the present invention, by using low viscosity and highly polar solvent, and in a solvent by adjusting solute
Concentration reduces the freezing point of solution, obtains with low solid-state temperature（Less than -100 DEG C）And the electrolysis of high ionic conductivity
Liquid；The electrolyte is used in metal secondary batteries, electrode material and electrolyte interface Charge-transfer resistance can be significantly reduced,
Additionally, due to the formation of not SEI, the internal resistance of metal secondary batteries greatly reduces, so that metal secondary batteries are at low temperature
Still excellent energy density and power density can be kept.
Description of the drawings
The present invention will be further described in detail below in conjunction with the accompanying drawings；
Fig. 1 is the flow diagram of the preparation method of ultralow temperature electrolyte provided by the invention；
Fig. 2 is a kind of flow diagram of the preparation method of ultralow temperature battery provided by the invention；
Fig. 3 is a kind of first circle charge and discharge electrical schematic for ultralow temperature battery that the embodiment of the present invention five provides；
Fig. 4 is a kind of charge and discharge cycles schematic diagram for ultralow temperature battery that the embodiment of the present invention five provides.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments；Based on the embodiments of the present invention, ordinary skill people
The every other embodiment that member is obtained without creative efforts, shall fall within the protection scope of the present invention.
Fig. 1 is the flow diagram of the preparation method of ultralow temperature electrolyte provided by the invention, as shown in Figure 1, ultralow temperature
The preparation method of electrolyte, including：By viscosity 0 ~ 2.0Between or dielectric constant >=30Aqueous solution, as
Solvent；To solubility >=3 in waterMetal salt, as electrolytic salt；Electrolytic salt is added in a solvent；Stirring is simultaneously
It is uniformly mixed, it is 3 ~ 25 to obtain mass concentrationElectrolyte.
Ultralow temperature electrolyte prepared by the preparation method of the ultralow temperature electrolyte provided through the invention, including：In solvent
The mass concentration of middle addition electrolytic salt, acquisition is 3 ~ 25Electrolyte；Wherein：The solvent is：Viscosity 0 ~
2.0Between or dielectric constant >=30Single solvent or its mixed solvent；The electrolytic salt is：?
Solubility >=3 in above-mentioned selected solventMetal salt.
Specifically, in the preparation method of the ultralow temperature electrolyte and ultralow temperature electrolyte, the solvent is：Water, carbon
The combination of one or more of dimethyl phthalate, ethylene carbonate, diethyl carbonate, acetonitrile, ethyl acetate；
The electrolytic salt is：The electrolytic salt is：Trifluoromethanesulfonic acid lithium（Chemical formula is：, it is abbreviated as：
LiOTf））, it is double（Fluorine sulphonyl）Imine lithium（Chemical formula is：, it is abbreviated as：LiFSI）, it is double（Fluoroform sulphonyl）
Imine lithium（Chemical formula is：, be abbreviated as：LiTFSI）, it is double（Pentafluoroethyl group sulfonyl）Imino group lithium（Chemical formula
For：, be abbreviated as：LiBETI）One or more of combination.
The low-temperature electrolyte of the present invention, by using low viscosity and highly polar solvent, and by adjusting solute in solvent
In concentration reduce the freezing point of solution, obtain with low solid-state temperature（Less than -100 DEG C）And the electricity of high ionic conductivity
Solve liquid.
Ultralow temperature electrolyte provided by the invention is illustrated with several more specific embodiments below.
Embodiment one：
First, in the present embodiment one：It is trifluoromethanesulfonic acid lithium that the solvent, which selects deionized water, the electrolytic salt,
（LiOTf）；Secondly, in draught cupboard, the trifluoromethanesulfonic acid lithium quantified will be dissolved in deionized water, is stirred 30 minutes respectively,
It is configured to 1-11Electrolyte, obtain electrolyte system one.
In the present embodiment one, the solid-state temperature of gained electrolyte system one passes through differential scanning calorimetry（DSC）Analysis can
Know that its solid-state temperature is -86 DEG C；The ionic conductivity of the electrolyte of various concentration at different temperatures is shown in Table 1（Conductivity unit
For mS/cm）.
By data in table it is found that in the electrolyte system one that the present embodiment one provides, when molal weight is 5
When, electrolyte has highest conductivity.
Embodiment two：
First, in the present embodiment two：The solvent selects deionized water, and the electrolytic salt is double（Fluoroform sulphonyl）
Imine lithium（LiTFSI）；Secondly, in draught cupboard, respectively by quantitative pair（Fluoroform sulphonyl）Imine lithium is dissolved in deionized water
In, it stirs 30 minutes, is configured to 3-14Electrolyte, obtain electrolyte system two.
In the present embodiment two, the solid-state temperature of gained electrolyte system two passes through differential scanning calorimetry（DSC）Analysis can
Know that its solid-state temperature is -86 DEG C；The ionic conductivity of the electrolyte of various concentration at different temperatures is shown in Table 2（Conductivity unit
For mS/cm）.
By data in table it is found that in the electrolyte system two that the present embodiment two provides, when molal weight is 8
When, electrolyte has highest conductivity.
Embodiment three：
First, in the present embodiment three：The solvent is dimethyl carbonate（DMC）It is 1 in mass ratio with deionized water:1 mixing
Mixed solvent made of stirring evenly, the electrolytic salt are trifluoromethanesulfonic acid lithium（LiOTf）；Secondly, in draught cupboard, point
Quantitative trifluoromethanesulfonic acid lithium is not dissolved in the mixed solvent, stirs 3 hours, is configured to 5Electrolyte, obtain electricity
Solve liquid system three.
In the present embodiment three, the solid-state temperature of gained electrolyte system three passes through differential scanning calorimetry（DSC）Analysis can
Know that its solid-state temperature is -78 DEG C；The ionic conductivity of the electrolyte of various concentration at different temperatures is shown in Table 3（Conductivity unit
For mS/cm）.
Example IV：
First, in the present embodiment four：The solvent is dimethyl carbonate（DMC）It is 1 in mass ratio with deionized water:1 mixing
Mixed solvent made of stirring evenly, the electrolytic salt are double（Fluoroform sulphonyl）Imine lithium（LiTFSI）；Secondly, exist
In draught cupboard, respectively by quantitative pair（Fluoroform sulphonyl）Imine lithium is dissolved in the mixed solvent, stirs 3 hours, is configured to 8 Electrolyte, obtain electrolyte system four.
In the present embodiment four, the solid-state temperature of gained electrolyte system four passes through differential scanning calorimetry（DSC）Analysis can
Know that its solid-state temperature is -113 DEG C；The ionic conductivity of the electrolyte of various concentration at different temperatures is shown in Table 4（Conductivity unit
For mS/cm）.
Fig. 2 is a kind of flow diagram of the preparation method of ultralow temperature lithium battery provided by the invention；As shown in Fig. 2, a kind of super
The preparation method of low temperature lithium battery, including：Positive active material, the first conductive material and first binder are added into solvent,
The first electrode slurry is obtained after mixing, the first electrode slurry is coated uniformly on the first collector, and roll-in after drying obtains
Positive plate；Negative electrode active material, the second conductive material and the second binder are added into solvent, obtains second electrode after mixing
The second electrode slurry is coated uniformly on the second collector by slurry, and roll-in after drying obtains negative plate；By the anode of preparation
Piece, negative plate, diaphragm are assembled in battery case；Electrolyte is injected into battery case, obtains ultralow temperature battery；Wherein, institute
Stating electrolyte is：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；Described is molten
Agent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Aqueous solution；The electrolytic salt is：It is molten
Xie Du >=3Metal salt.
By applying the ultralow temperature electrolyte in the present invention in metal secondary batteries, electrode material can be significantly reduced
With electrolyte interface Charge-transfer resistance, additionally, due to the formation of not SEI, the internal resistance of metal secondary batteries greatly reduces, from
And metal secondary batteries is made still can to keep excellent energy density and power density at low temperature.
Specifically, the positive active material that the anode uses for：、 、、、AndIn one or several kinds of compounds combination；
The negative electrode active material that the cathode uses for：、、 、
In one or several kinds of compounds combination；Wherein：In compound：M it is separate for Fe, Co, Ni, Mn, Mo, Mg, Cu,
Any one in Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Specifically, the solvent is N-Methyl pyrrolidone；First conductive material used, the second conductive material are conduction
Carbon black；First binder used, the second binder are Kynoar（PVDF）, polytetrafluoroethylene (PTFE)（（PTFE）In it is arbitrary
It is a kind of；The positive active material, conductive black, binder mass ratio be 92:5:3.
A kind of ultralow temperature lithium battery prepared by a kind of preparation method of the ultralow temperature lithium battery provided through the invention, packet
It includes：Anode, cathode, diaphragm and the electrolyte being arranged in battery case；The electrolyte is：Electrolyte is added in a solvent
The mass concentration of salt, acquisition is 3 ~ 25Electrolyte；The solvent is：Viscosity is 0 ~ 2.0Between, or
Dielectric constant >=30Aqueous solution；The electrolytic salt is：Solubility >=3Metal salt.
The ultralow temperature battery of the present invention uses above-mentioned ultralow temperature electrolyte, significantly improves under metal ion battery low temperature
Charge/discharge capacity conservation rate and charging/discharging voltage platform have excellent cryogenic property.
The positive active material that the anode uses for：、 、、、AndIn one or several kinds of compounds combination；What the cathode used
Negative electrode active material is：、、 、In it is a kind of or several
The combination of kind compound；Wherein：In compound：M it is separate for Fe, Co, Ni, Mn, Mo, Mg, Cu, Zn, Al, Sn, B, Ga,
Any one in Cr, Sr, V, Ti；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
The preparation method of ultralow temperature battery provided by the invention is illustrated with several more specific embodiments below.
Embodiment five：
In the present embodiment five, the electrolyte is：The electrolyte that embodiment one provides；The positive active material that anode uses
For：；Negative electrode active material used in cathode is： 。
The step of preparation method for the ultralow temperature battery that the present embodiment five provides, is as follows：
1）The preparation of anode；It is 90 by mass ratio:7:3 positive electrode, the first conductive material（Conductive black）,
First binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the first electrode slurry（Anode slurry
Material）, this slurry is coated uniformly on the first collector（Stainless steel collector）On, it is dry after roll-in obtain anode pole piece；
2）The preparation of cathode；It is 90 by mass ratio:7:3 negative material, the second conductive material（Conductive charcoal
It is black）, the second binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the second electrode slurry（It is negative
Pole slurry）, this slurry is coated uniformly on the second collector（Stainless steel collector）On, it is dry after roll-in obtain cathode pole piece；
3）Battery core assembles；Positive plate, diaphragm and negative plate are assembled into battery case；
4）The injection of electrolyte；The electrolyte that embodiment one provides is injected into battery case, obtains ultralow temperature battery.
Under condition of different temperatures, in the operating voltage section of 0 ~ 2.0V with 0.5C（1C=120mA/g）Current strength, into
Row charge and discharge cycles are tested.
Test result is as follows：First discharge specific capacity is 51, average voltage 1.5V, full battery is than energy
76 （As shown in Figure 3：Ultralow temperature battery is in -40 DEG C, the first circle charge and discharge electrical schematic of 0.5C）, with 1C current densities into
Row charge and discharge cycles, after 200 times recycle, capacity retention ratio 96%, coulombic efficiency 99.9%（As shown in Figure 4：Ultralow temperature electricity
Pond is in -40 DEG C, the charge and discharge cycles schematic diagram of 1C）.
Battery capacity conservation rate is shown in Table 5.
Embodiment six：
In the present embodiment six, the electrolyte is：The electrolyte that embodiment one provides；The positive active material that anode uses
For：；Negative electrode active material used in cathode is： 。
The step of preparation method for the ultralow temperature battery that the present embodiment six provides, is as follows：
1）The preparation of anode；It is 90 by mass ratio:7:3 positive electrode, the first conductive material（Conductive charcoal
It is black）, first binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the first electrode slurry（Just
Pole slurry）, this slurry is coated uniformly on the first collector（Stainless steel collector）On, it is dry after roll-in obtain anode pole piece；
2）The preparation of cathode；It is 90 by mass ratio:7:3 negative material, the second conductive material（Conductive charcoal
It is black）, the second binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the second electrode slurry（It is negative
Pole slurry）, this slurry is coated uniformly on the second collector（Stainless steel collector）On, it is dry after roll-in obtain cathode pole piece；
3）Battery core assembles；Positive plate, diaphragm and negative plate are assembled into battery case；
4）The injection of electrolyte；The electrolyte that embodiment one provides is injected into battery case, obtains ultralow temperature battery.
Under condition of different temperatures, in the operating voltage section of 0 ~ 2.0V with 0.5C（1C=120mA/g）Current strength, into
Row charge and discharge cycles are tested.
Test result is as follows：First discharge specific capacity is 63, average voltage 1V, full battery is 63 than energy, charge and discharge cycles are carried out with 1C current densities, after 200 cycles, capacity retention ratio 97%, coulombic efficiency is
99.9%。
Battery capacity conservation rate is shown in Table 6.
Embodiment seven：
In the present embodiment seven, the electrolyte is：The electrolyte that embodiment two provides；The positive active material that anode uses
For：；Negative electrode active material used in cathode is： 。
The step of preparation method for the ultralow temperature battery that the present embodiment seven provides, is as follows：
1）The preparation of anode；It is 90 by mass ratio:7:3 positive electrode, the first conductive material（Conductive black）,
First binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the first electrode slurry（Anode slurry
Material）, this slurry is coated uniformly on the first collector（Stainless steel collector）On, it is dry after roll-in obtain anode pole piece；
2）The preparation of cathode；It is 90 by mass ratio:7:3 negative material, the second conductive material（Conductive charcoal
It is black）, the second binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the second electrode slurry（It is negative
Pole slurry）, this slurry is coated uniformly on the second collector（Stainless steel collector）On, it is dry after roll-in obtain cathode pole piece；
3）Battery core assembles；Positive plate, diaphragm and negative plate are assembled into battery case；
4）The injection of electrolyte；The electrolyte that embodiment two provides is injected into battery case, obtains ultralow temperature battery.
Under condition of different temperatures, in the operating voltage section of 0 ~ 2.0V with 0.5C（1C=120mA/g）Current strength, into
Row charge and discharge cycles are tested.
Test result is as follows：First discharge specific capacity is 49, average voltage 1.5V, full battery is than energy
74 ；Charge and discharge cycles are carried out with 1C current densities, and after 200 cycles, capacity retention ratio 96%, coulombic efficiency is
99.9%。
Battery capacity conservation rate is shown in Table 7.
Embodiment eight：
In the present embodiment eight, the electrolyte is：The electrolyte that embodiment two provides；The positive active material that anode uses
For：；Negative electrode active material used in cathode is： 。
The step of preparation method for the ultralow temperature battery that the present embodiment seven provides, is as follows：
1）The preparation of anode；It is 90 by mass ratio:7:3 positive electrode, the first conductive material（Conductive charcoal
It is black）, first binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the first electrode slurry（Just
Pole slurry）, this slurry is coated uniformly on the first collector（Stainless steel collector）On, it is dry after roll-in obtain anode pole piece；
2）The preparation of cathode；It is 90 by mass ratio:7:3 negative material, the second conductive material（Conductive charcoal
It is black）, the second binder（PVDF）, it is separately added into solvent N-methyl pyrilidone, is uniformly mixed and obtains the second electrode slurry（It is negative
Pole slurry）, this slurry is coated uniformly on the second collector（Stainless steel collector）On, it is dry after roll-in obtain cathode pole piece；
3）Battery core assembles；Positive plate, diaphragm and negative plate are assembled into battery case；
4）The injection of electrolyte；The electrolyte that embodiment two provides is injected into battery case, obtains ultralow temperature battery.
Under condition of different temperatures, in the operating voltage section of 0 ~ 2.0V with 0.5C（1C=120mA/g）Current strength, into
Row charge and discharge cycles are tested.
Test result is as follows：First discharge specific capacity is 63, average voltage 1V, full battery is 63 than energy；Charge and discharge cycles are carried out with 1C current densities, and after 200 cycles, capacity retention ratio 97%, coulombic efficiency is
99.9%。
Battery capacity conservation rate is shown in Table 8.
Ultralow temperature electrolyte provided by the invention and preparation method thereof and the battery using the ultralow temperature electrolyte and its preparation
Method is suitable for the metal secondary batteries such as multiple battery system, such as sodium, potassium, zinc, manganese, magnesium, aluminium-air cell.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. ultralow temperature electrolyte, it is characterised in that：Including：
Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；
Wherein：The solvent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Single solvent, or
Its mixed solvent；
The electrolytic salt is：Solubility >=3 in above-mentioned selected solventMetal salt.
2. ultralow temperature electrolyte according to claim 1, it is characterised in that：The solvent is：Water, dimethyl carbonate, carbon
The combination of one or more of vinyl acetate, diethyl carbonate, acetonitrile, ethyl acetate.
3. ultralow temperature electrolyte according to claim 1, it is characterised in that：The electrolytic salt is：Trifluoromethanesulfonic acid lithium,
It is double（Fluorine sulphonyl）It is imine lithium, double（Fluoroform sulphonyl）It is imine lithium, double（Pentafluoroethyl group sulfonyl）One kind in imino group lithium or
The a variety of combination of person.
4. the preparation method of ultralow temperature electrolyte, it is characterised in that：Including：
By viscosity 0 ~ 2.0Between or dielectric constant >=30Aqueous solution, as solvent；
To solubility >=3 in waterMetal salt, as electrolytic salt；
Electrolytic salt is added in a solvent；
It stirs and is uniformly mixed, it is 3 ~ 25 to obtain mass concentrationElectrolyte.
5. ultralow temperature lithium battery, it is characterised in that：Including：Anode, cathode, diaphragm and the electrolyte being arranged in battery case；
The electrolyte is：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolyte；It is described
Solvent be：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Aqueous solution；The electrolytic salt is：
Solubility >=3Metal salt.
6. ultralow temperature lithium battery according to claim 5, it is characterised in that：
The positive active material that the anode uses for：、、、、AndIn one or several kinds of compounds combination；
The negative electrode active material that the cathode uses for：、、、In one or several kinds of compounds combination；
Wherein：In compound：M separate is Fe, Co, Ni, Mn, Mo, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti
In any one；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
7. the preparation method of ultralow temperature lithium battery, it is characterised in that：Including：
The preparation of anode；Specially：Positive active material, the first conductive material and first binder, mixing are added into solvent
The first electrode slurry is obtained after uniformly, the first electrode slurry is coated uniformly on the first collector, and roll-in after drying obtains anode
Piece；
The preparation of cathode；Specially：Negative electrode active material, the second conductive material and the second binder, mixing are added into solvent
The second electrode slurry is obtained after uniformly, the second electrode slurry is coated uniformly on the second collector, and roll-in after drying obtains cathode
Piece；
The positive plate, negative plate, diaphragm of preparation are assembled in battery case；
Electrolyte is injected into battery case, obtains ultralow temperature battery；
Wherein, the electrolyte is：Electrolytic salt is added in a solvent, the mass concentration of acquisition is 3 ~ 25Electrolysis
Liquid；The solvent is：Viscosity is 0 ~ 2.0Between or dielectric constant >=30Aqueous solution；The electrolyte
Salt is：Solubility >=3Metal salt.
8. the preparation method of ultralow temperature lithium battery according to claim 1, it is characterised in that：
The positive active material that the anode uses for：、、、、AndIn one or several kinds of compounds combination；
The negative electrode active material that the cathode uses for：、、、In one or several kinds of compounds combination；
Wherein：In compound：M separate is Fe, Co, Ni, Mn, Mo, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti
In any one；And 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
9. the preparation method of ultralow temperature lithium battery according to claim 1, it is characterised in that：The solvent is N- methyl pyrroles
Pyrrolidone；First conductive material used, the second conductive material are conductive black；First binder used, the second binder are equal
For any one in Kynoar, polytetrafluoroethylene (PTFE).
10. the preparation method of ultralow temperature lithium battery according to claim 1, it is characterised in that：The positive active material,
Conductive black, binder mass ratio be 92:5:3.
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