CN109818055A - Electrolyte solution for preventing thermal runaway in wide temperature range and secondary lithium battery composed thereof - Google Patents
Electrolyte solution for preventing thermal runaway in wide temperature range and secondary lithium battery composed thereof Download PDFInfo
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Abstract
本发明涉及锂电池电解液，具体的说是一种宽温区防热失控的电解液及其构成的二次锂电池。宽温区防热失控电解液包括锂盐、一种或多种聚合物单体、添加剂、溶剂和催化剂。聚合物单体在高温下发生聚合反应，使液态电解液变为聚合物电解质，电解质在200℃高温下仍然稳定存在。部分聚合单体具有低的熔点，在‑60℃环境中保持液态。与传统碳酸酯类电解液相比，本发明提供的宽温区防热失控的电解液，在较宽的温度范围内（‑40~200℃）表现出较高的离子电导率，闪点燃点高。与常规电池的电解液相比，在宽温下具有良好的长循环稳定性，并且能够在高温下起到防止电池热失控的作用。The invention relates to a lithium battery electrolyte, in particular to a wide temperature region thermal runaway-proof electrolyte and a secondary lithium battery formed thereof. The wide temperature range thermal runaway protection electrolyte includes a lithium salt, one or more polymer monomers, additives, solvents and catalysts. The polymer monomer undergoes a polymerization reaction at high temperature, so that the liquid electrolyte becomes a polymer electrolyte, and the electrolyte still exists stably at a high temperature of 200 °C. Partially polymerized monomers have low melting points and remain liquid at ‑60°C. Compared with the traditional carbonate electrolyte, the electrolyte with wide temperature range to prevent thermal runaway provided by the present invention exhibits higher ionic conductivity and flash point in a wider temperature range (-40~200°C). high. Compared with the electrolyte of conventional batteries, it has good long-term cycle stability at a wide temperature, and can prevent the thermal runaway of the battery at high temperature.
Description
Technical field
The invention belongs to the electrolyte and its composition of technical field of lithium batteries more particularly to a kind of anti-thermal runaway of wide warm area
Serondary lithium battery.
Background technique
In recent years due to shortage of resources and environmental pollution, the novel industrial technology such as electric car is rapidly developed, to high-performance
The demand of lithium ion battery is also more more and more urgent.Currently, commercial serondary lithium battery electrolyte is mainly by ethylene carbonate, carbonic acid
Dimethyl ester, diethyl carbonate and lithium hexafluoro phosphate mix.Wherein, since 60 DEG C of lithium hexafluoro phosphate or more can decompose,
The carbonate-based solvents such as dimethyl carbonate are low-flash, volatile organic solvent, have limited to the use temperature range of lithium battery,
Also seriously affected the high temperature safe performance of lithium battery, so hamper serondary lithium battery automobile power cell, aerospace,
It applies on a large scale mobile base station etc..Relative to liquid electrolyte, polymer dielectric be can reduce present in liquid electrolyte
Leakage pollution and combustion explosion, fundamentally solve serondary lithium battery security risk.Meanwhile polymer dielectric is in high temperature
There is down excellent battery performance.CN107887643A patent discloses a kind of consolidating for POSS base ionic liquid of solid-state containing high temperature resistant
State polymer dielectric, which has excellent High Temperature ionic Conductivity, but its room-temperature conductivity is relatively low.
CN106532116A discloses a kind of polymer dielectric resistant to high temperature, and ethylene oxide segment is contained in polymer chain architecture, is gathered
One or more of carbonic ester segment, the polymer dielectric have high thermal decomposition temperature, but its impedance at room temperature
Greatly, the serondary lithium battery of assembling is only capable of carrying out charge and discharge cycles with low current at room temperature.It is warm in order to widen using for electrolyte
Degree, we prepare the electrolyte of wide warm area using the monomer that polymerization reaction can occur at high temperature.The electrolyte is in room temperature and low
It is liquid under warm (- 60 DEG C), there is high conductivity at room temperature, excellent cycle performance and high rate performance.At high temperature, electric
Polymerization reaction can occur for the ether solvent in solution liquid, improve electrolyte high-temperature stability.At the same time, when battery reaches diaphragm heat
When contraction or melt temperature, due to the presence of polymer dielectric, additionally it is possible to the generation of internal short-circuit is effectively prevented, to reach
To the purpose of prevention battery thermal runaway.
Summary of the invention
The purpose of the present invention is to provide a kind of anti-thermal runaway electrolyte of width warm area and its serondary lithium batteries of composition.
A kind of the technical solution adopted by the present invention to achieve the above object are as follows: the serondary lithium battery electricity of the anti-thermal runaway of width warm area
Liquid is solved, electrolyte includes lithium salts, one or more polymerized monomers, additive, solvent and catalyst, and polymerized monomer is in the electrolytic solution
Mass fraction be 1%-90%, the mass fraction of lithium salts in the electrolytic solution is 5%-80%, the quality of additive in the electrolytic solution point
Number is 0 ~ 50%, and the mass fraction of solvent in the electrolytic solution is 0 ~ 50%, and the mass fraction of catalyst in the electrolytic solution is 0 ~ 5%.
The polymerized monomer has the chain structure of general formula 1 or general formula 2.
General formula 1,
R1For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R2For CH2、C2H4、CF2、C2F4、CCl2、C2Cl4、CBr2、C2Br4One kind；
R3For CH2、CF2、CCl2、CBr2One kind；
R4For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R1And R4It is not simultaneously alkyl, the numerical value that the numerical value of m is 1 ~ 5000, n is 1 ~ 10；
General formula 2
R5For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R6For CH2、CF2、CCl2、CBr2One kind；
R7For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R5And R7It is not simultaneously alkyl, the numerical value that the numerical value of j is 1 ~ 5000, i is 1 ~ 10；
The lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, hexafluoroarsenate lithium, tetrafluoro
Lithium borate, trifluoromethyl sulfonic acid lithium, double fluoromethane sulfimide lithiums one or several kinds；
The additive is one of flame-retardant additive and film for additive or two kinds；Wherein, flame-retardant additive is phosphoric acid
Trimethyl, triethyl phosphate, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester, diphenyl octyl phosphate, pivaloyl amine, three
Paracyanogen acid triallyl, triallyl isocyanate, gamma-butyrolacton, fluorinated ethylene carbonate, three fluoropropylene carbonates, 1,
Tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ether of 1,2,2-, vinyl-three-(methyl ethyl ketone oxime) silane, aminomethyl phenyl dimethyl
One or more of diethoxy silane；Film for additive is acetic anhydride, vinylacetate, three (trimethyl silane) phosphoric acid
Ester, allylic carbon acetoacetic ester, methanesulfonic acid propynyl ester, tetrachloro-ethylene, sulfuric acid vinyl ester, 2- phenylimidazole, maleimide, sulfurous
The bromo- benzyl isocyanate ester of vinyl acetate, catechol carbonic ester, 4-, thiophene, 3,4- ethylenedioxythiophene, two silicon of hexamethyl
One or more of oxygen alkane, N- methylpyrrole, ortho-terphenyl, dimethyl acetamide, lithium nitrate, vinylene carbonate；
The solvent is triethylene glycol dimethyl ether, in tetraethyleneglycol dimethyl ether, five ethylene glycol dimethyl ether, succinonitrile, glutaronitrile
It is one or more of；
The catalyst be azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, dibenzoyl peroxide,
N, N- dimethylaniline, n-BuLi, lithium powder, naphthalene sodium, cumyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide,
One or more of tert-butyl hydroperoxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate；
Preferred technical solution are as follows:
R in polymerized monomer general formula 11、R4For one kind of acrylate-based, carbon-carbon double bond or sulfydryl；R1And R4It is not simultaneously alkane
Base, R2For CH2、C2H4、CF2Or C2F4One kind, R3For CH2Or CF2One kind, m is that 1 ~ 1000, n is 1 ~ 5；R in general formula 25、
R7For one kind of acrylate-based, carbon-carbon double bond or sulfydryl；R5And R7It is not all alkyl, R6For CH2Or CF2One kind, j be 1 ~
1000, i be 1 ~ 5；The mass fraction of polymerized monomer in the electrolytic solution is 2% ~ 80%.
Lithium salts is one of difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate, lithium perchlorate；The matter of lithium salts in the electrolytic solution
Measuring score is 5% ~ 30%；
The mass fraction of additive in the electrolytic solution is 0.5 ~ 50%；
The mass fraction of solvent in the electrolytic solution is 10 ~ 40%；
The mass fraction of catalyst in the electrolytic solution is 0.01% ~ 3%.
Preferred technical solution are as follows:
End group contains the R in the ethers general formula 1 of reactable functional group1、R4For acrylate-based or carbon-carbon double bond one kind；R1
And R4It is not all alkyl, R2For CH2Or C2H4One kind, R3For CH2；M is that 5 ~ 100, n is 1 ~ 3；R in general formula 25、R7For propylene
One kind of perester radical or carbon-carbon double bond；R5And R7It is not all alkyl, R6For CH2；J is that 5 ~ 100, i is 1 ~ 3；Polymerized monomer is being electrolysed
Mass fraction in liquid is 5% ~ 60%；
Lithium salts is one of difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate；The mass fraction of lithium salts in the electrolytic solution be 9% ~
30%；
The mass fraction of additive in the electrolytic solution is 0.5 ~ 30%；
The mass fraction of solvent in the electrolytic solution is 10 ~ 30%；
The mass fraction of catalyst in the electrolytic solution is 0.05% ~ 2%.
A kind of a kind of preparation method of the serondary lithium battery electrolyte of the anti-thermal runaway of wide warm area described above, step
Are as follows:
1) one or more than one kinds of polymerized monomers, additive, solvent, catalyst are mixed in a certain ratio, are stirred to complete
Dissolution；
2) lithium salts is added in Xiang Shangshu uniform solution, continues stirring after addition to being completely dissolved, obtains the anti-thermal runaway electricity of wide warm area
Solve liquid；The mass fraction of polymerized monomer in the electrolytic solution is 1%-90%, and the mass fraction of lithium salts in the electrolytic solution is 5%-80%, is added
Adding the mass fraction of agent in the electrolytic solution is 0 ~ 50%, and the mass fraction of solvent in the electrolytic solution is 0 ~ 50%, and catalyst is being electrolysed
Mass fraction in liquid is 0 ~ 5%.
The polymerized monomer has the chain structure of general formula 1 or general formula 2.
General formula 1
R1For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R2For CH2、C2H4、CF2、C2F4、CCl2、C2Cl4、CBr2、C2Br4One kind；
R3For CH2、CF2、CCl2、CBr2One kind；
R4For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R1And R4It is not simultaneously alkyl, the numerical value that the numerical value of m is 1 ~ 5000, n is 1 ~ 10；
General formula 2
R5For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R6For CH2、CF2、CCl2、CBr2One kind；
R7For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R5And R7It is not simultaneously alkyl, the numerical value that the numerical value of j is 1 ~ 5000, i is 1 ~ 10；
The lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, hexafluoroarsenate lithium, tetrafluoro
Lithium borate, trifluoromethyl sulfonic acid lithium, double fluoromethane sulfimide lithiums one or several kinds；
The additive includes flame-retardant additive and film for additive；Wherein, flame-retardant additive is trimethyl phosphate, tricresyl phosphate second
Ester, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester, diphenyl octyl phosphate, pivaloyl amine, triallyl cyanurate,
Triallyl isocyanate, gamma-butyrolacton, fluorinated ethylene carbonate, three fluoropropylene carbonates, tetra- fluoro ethyl of 1,1,2,2--
2,2,3,3- tetrafluoro propyl ether, vinyl-three-(methyl ethyl ketone oxime) silane, in aminomethyl phenyl dimethyl diethoxysilane
One or more；Film for additive is acetic anhydride, vinylacetate, three (trimethyl silane) phosphates, allyl carbonate second
Ester, methanesulfonic acid propynyl ester, tetrachloro-ethylene, sulfuric acid vinyl ester, 2- phenylimidazole, maleimide, ethylene sulfite, adjacent benzene two
The bromo- benzyl isocyanate ester of phenol carbonic ester, 4-, thiophene, 3,4- ethylenedioxythiophene, hexamethyldisiloxane, N- methyl pyrrole
It coughs up, one or more of ortho-terphenyl, dimethyl acetamide, lithium nitrate, vinylene carbonate；
The solvent is triethylene glycol dimethyl ether, in tetraethyleneglycol dimethyl ether, five ethylene glycol dimethyl ether, succinonitrile, glutaronitrile
It is one or more of；
The catalyst be azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, dibenzoyl peroxide,
N, N- dimethylaniline, n-BuLi, lithium powder, naphthalene sodium, cumyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide,
One or more of tert-butyl hydroperoxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate；
Preferred technical solution are as follows:
R in polymerized monomer general formula 11、R4For one kind of acrylate-based, carbon-carbon double bond or sulfydryl；R1And R4It is not all alkyl,
R2For CH2、C2H4、CF2Or C2F4One kind, R3For CH2Or CF2One kind, m is that 1 ~ 1000, n is 1 ~ 5；R in general formula 25、R7For
One kind of acrylate-based, carbon-carbon double bond or sulfydryl；R5And R7It is not all alkyl, R6For CH2Or CF2One kind, j be 1 ~ 1000, i
It is 1 ~ 5；The mass fraction of polymerized monomer in the electrolytic solution is 2% ~ 80%.
Lithium salts is one of difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate, lithium perchlorate；The matter of lithium salts in the electrolytic solution
Measuring score is 5% ~ 30%；
The mass fraction of additive in the electrolytic solution is 0.5 ~ 50%；
The mass fraction of solvent in the electrolytic solution is 10 ~ 40%；
The mass fraction of catalyst in the electrolytic solution is 0.01% ~ 3%.
Preferred technical solution are as follows:
End group contains the R in the ethers general formula 1 of reactable functional group1、R4For acrylate-based or carbon-carbon double bond one kind；R1
And R4It is not all alkyl, R2For CH2Or C2H4One kind, R3For CH2；M is that 5 ~ 100, n is 1 ~ 3；R in general formula 25、R7For propylene
One kind of perester radical or carbon-carbon double bond；R5And R7It is not all alkyl, R6For CH2；J is that 5 ~ 100, i is 1 ~ 3；Polymerized monomer is being electrolysed
Mass fraction in liquid is 5% ~ 60%；
Lithium salts is one of difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate；The mass fraction of lithium salts in the electrolytic solution be 9% ~
30%；
The mass fraction of additive in the electrolytic solution is 0.5 ~ 30%；
The mass fraction of solvent in the electrolytic solution is 10 ~ 30%；
The mass fraction of catalyst in the electrolytic solution is 0.05% ~ 2%.
A kind of application of the anti-thermal runaway electrolyte of wide warm area described above in serondary lithium battery.
Further, the wide anti-thermal runaway electrolyte of warm area is preparing lithium metal battery, lithium ion battery or lithium-sulphur
Application in battery.
A kind of serondary lithium battery, including anode, cathode, diaphragm, the electrolyte between positive and negative anodes, it is characterised in that:
The electrolyte is wide warm area heat release described above electrolyte out of control；The active material of the anode is cobalt acid lithium, phosphorus
Sour iron lithium, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, ternary material, sulphur, sulfur compound, ferric sulfate lithium, lithium ion fluorophosphoric acid
One of salt, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide；The active material of cathode is lithium metal, lithium metal
Alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony carbon composite, tin antimony composite material, lithium titanyl
One of compound；The diaphragm material is cellulosic separator, in polypropylene diaphragm, polyethylene diagrams, fibreglass diaphragm
It is a kind of.
A kind of preparation of serondary lithium battery, it is characterised in that: separated positive and negative anodes pole piece with diaphragm, between positive cathode
Wide warm area heat release described above electrolyte out of control is added, seals to obtain serondary lithium battery.
Advantage for present invention:
Using polymerized monomer as electrolyte component, polymerization reaction can occur at high temperature, make liquid electrolyte the present invention for polymerized monomer
Liquid becomes polymer dielectric at high temperature, prevents the high temperature of electrolyte from revealing, and keeps electrolyte still steady under 200 DEG C of high temperature
It is fixed to exist, have the function that improve electrolyte high-temperature stability and prevents battery thermal runaway.At the same time, partially polymerized monomer tool
There is low fusing point, keep liquid in -60 DEG C of environment, electrolyte ionic conductivity with higher at low temperature can be made, opened up
The low temperature of wide serondary lithium battery uses temperature.In wide temperature range, electrolyte shows high ionic conductivity and Gao An
Quan Xing, and electrolyte is nontoxic, environmental-friendly, is of great significance for serondary lithium battery large-scale application.The electrolyte can answer
For lithium metal battery, lithium ion battery or lithium-sulfur cell.
Detailed description of the invention
Fig. 1 be with embodiment 1 be electrolyte assembling LiFePO4The charging and discharging curve of/Li battery.
Fig. 2 be with embodiment 2 be electrolyte assembling LiFe0.2Mn0.8PO4Long circulating of/Li the battery under 120 DEG C of high temperature
Curve.
Fig. 3 be with embodiment 3 be electrolyte assembling LiCoO2The long circulating curve under -40 DEG C of low temperature of/Li battery.
Specific embodiment
In order to protrude objects and advantages of the present invention, the present invention is described by the following specific embodiments, but of the invention
It is not limited to following embodiment.
Embodiment 1
It, will under the conditions of anhydrous and oxygen-free(R1To be acrylate-based, R2For methyl, R3For ethyl, R4
For methyl, m=10, n=2) with difluorine oxalic acid boracic acid lithium be made into the electrolyte that molar concentration is 1mol/L.The heatproof model of the electrolyte
Enclosing is -20 DEG C ~ 300 DEG C, the LiFePO of assembling4/ Li button cell room temperature specific discharge capacity is 168mAh/g, -40 DEG C of electric discharge
Specific capacity is 120mAh/g, and the specific discharge capacity that 100 DEG C of high temperature is 140mAh/g.
Embodiment 2
It, will under the conditions of anhydrous and oxygen-free(R1, R2For ethyl, R3For methyl, R4For carbon-carbon double bond, m
=20, n=1) it is dissolved with lithium nitrate, triethylene glycol dimethyl ether according to the ratio of 5:0.5:4.5, then be made into lithium hexafluoro phosphate
The electrolyte of 1mol/L.The temperature resistant range of the electrolyte is -60 DEG C ~ 160 DEG C, the LiFe of assembling0.2Mn0.8PO4/ Li button cell
Room temperature specific discharge capacity is 158mAh/g, and -50 DEG C of specific discharge capacity is 140mAh/g, and the specific discharge capacity of high temperature of 120 DEG C is
132mAh/g。
Embodiment 3
It, will under the conditions of anhydrous and oxygen-free(R5, R6For methyl, R7For carbon-carbon double bond, j=50, i=2)
It is dissolved with trimethyl phosphate according to 5:5 ratio, then dissolves in the lithium perchlorate that molar concentration is 1mol/L.The heatproof model of the electrolyte
Enclosing is -50 DEG C ~ 200 DEG C, the LiCoO of assembling2/ Li button cell room temperature specific discharge capacity is 158mAh/g, -40 DEG C of electric discharge ratio
Capacity is 120mAh/g, and the specific discharge capacity that 90 DEG C of high temperature is 160mAh/g.
Embodiment 4
It, will under the conditions of anhydrous and oxygen-free(R5For carbon-carbon double bond, R6For ethyl, R7For epoxy group, m=
20, n=1) it is dissolved with triphenyl phosphate, vinylene carbonate according to the ratio of 4:5:1, then dissolving in molar concentration is 1mol/L's
Difluorine oxalic acid boracic acid lithium.The temperature resistant range of the electrolyte is -40 DEG C ~ 200 DEG C, the LiFePO of assembling4/ Li button cell room temperature is put
Electric specific capacity is 148mAh/g, and -40 DEG C of specific discharge capacity is 120mAh/g, and the specific discharge capacity that 110 DEG C of high temperature is 160mAh/
g。
Embodiment 5
It, will under the conditions of anhydrous and oxygen-free(R1For epoxy group, R2For methyl, R3For ethyl, R4For carbon
Carbon double bond, m=1000, n=2) with(R5For carbon-carbon double bond, R6For ethyl, R7For epoxy group, m=20, n
=1) it is dissolved according to 1:1 ratio, then dissolves in the difluorine oxalic acid boracic acid lithium that molar concentration is 1mol/L.The temperature resistant range of the electrolyte
It is -20 DEG C ~ 180 DEG C, the LiFe of assembling0.2Mn0.8PO4/ Li button cell room temperature specific discharge capacity is 152mAh/g, -20 DEG C
Specific discharge capacity is 110mAh/g, and the specific discharge capacity that 130 DEG C of high temperature is 160mAh/g.
Embodiment 6
It, will under the conditions of anhydrous and oxygen-free(R1To be acrylate-based, R2For methyl, R3For ethyl, R4
For methyl, m=10, n=2) and fluorinated ethylene carbonate, allylic carbon acetoacetic ester, five ethylene glycol dimethyl ether, dicetyl peroxydicarbonate two
Isopropyl ester is dissolved according to the ratio of 5:0.25:4.5:0.25, then being made into molar concentration with difluorine oxalic acid boracic acid lithium is 2mol/L's
Electrolyte.The temperature resistant range of the electrolyte is -40 DEG C ~ 200 DEG C, the LiFePO of assembling4/ Li button cell room temperature specific discharge capacity
For 150mAh/g, -40 DEG C of specific discharge capacity is 100mAh/g, and the specific discharge capacity that 100 DEG C of high temperature is 160mAh/g.
Embodiment 7
It, will under the conditions of anhydrous and oxygen-free(R5, R6For methyl, R7For carbon-carbon double bond, j=50, i=2)
With fluorinated ethylene carbonate, allylic carbon acetoacetic ester, five ethylene glycol dimethyl ether, di-isopropyl peroxydicarbonate according to 3:0.5:
The ratio of 6:0.5 dissolves, then is made into the electrolyte that molar concentration is 4mol/L with difluorine oxalic acid boracic acid lithium.The heatproof of the electrolyte
Range is -30 DEG C ~ 200 DEG C, the LiFePO of assembling4/ Li button cell room temperature specific discharge capacity is 162mAh/g, and -40 DEG C put
Electric specific capacity is 90mAh/g, and the specific discharge capacity that 100 DEG C of high temperature is 163mAh/g.
Comparative experiments:
Just extremely LiFePO4, the button lithium battery that cathode is lithium, electrolyte are conventional electrolysis liquid (LiPF for assembling6/EC:DEC=
1:1), 1C multiplying power discharging, room temperature specific discharge capacity are 160mAh/g, and -20 DEG C of specific discharge capacities are 80mAh/g, 60 DEG C of high temperature with
Upper discharge capacity decaying quickly, can not carry out long circulating test.
Test battery performance the following steps are included:
(1) preparation of positive plate
Kynoar (PVDF) is dissolved in N by A, in N-2- methyl pyrrolidone, concentration 0.1mol/L.
After B mixes PVDF, positive electrode active materials, conductive black with the mass ratio of 10:80:10, grind at least 1 hour.
The resulting slurry of upper step is evenly coated on aluminium foil by C, with a thickness of 100 ~ 120 μm, is first dried at 60 DEG C, then
It is dried under 120 DEG C of vacuum drying ovens, roll-in, punching, continues to dry in 120 DEG C of vacuum drying ovens after weighing, be placed in glove box
It is spare.
D is cut by size.
(2) battery assembly
(3) battery charging/discharging performance testing
Test mode is as follows: with the charge and discharge for the serondary lithium battery that the test of LAND battery charge and discharge instrument is assembled by different ethers electrolyte
Curve and long circulating performance.
As seen from Figure 1, the LiFePO assembled by the electrolyte of embodiment 14/ Li battery has stable charge and discharge at room temperature
Level platform has lower polarizing voltage, about 168 mAh/g during 1C charge and discharge cycles.
From Figure 2 it can be seen that the LiFe assembled by the electrolyte of embodiment 20.2Mn0.8PO4/ Li battery energy under 120 DEG C of high temperature
Enough carry out stable long circulating.In the case where circulation 100 is enclosed, capacity is positively retained at 135mAh/g, shows in high temperature excellent
Long circulating stability.
As seen from Figure 3, the LiCoO assembled by the electrolyte of embodiment 32/ Li battery in -40 DEG C of low temperature, 100 circle of circulation
The specific discharge capacity of 120mAh/g is still maintained afterwards.
The LiFePO assembled in contrast to conventional commercial electrolyte liquid4/ Li battery, polymerized monomer electrolyte can at room temperature
Keep the specific discharge capacity to match in excellence or beauty with commercial electrolyte liquid phase.At low temperatures and high temperatures, especially under conditions of being higher than 60 DEG C, gather
The charge and discharge cycles that monomer electrolyte can be carried out steadily are closed, and show high specific discharge capacity, battery performance is obviously excellent
In commercial electrolyte liquid.
Claims (7)
1. a kind of serondary lithium battery electrolyte of the anti-thermal runaway of width warm area, it is characterised in that: electrolyte includes lithium salts, one kind or more
Kind polymerized monomer, additive, solvent and catalyst, the mass fraction of polymerized monomer in the electrolytic solution are 1%-90%, and lithium salts is in electricity
Solving the mass fraction in liquid is 5%-80%, and the mass fraction of additive in the electrolytic solution is 0 ~ 50%, the matter of solvent in the electrolytic solution
Measuring score is 0 ~ 50%, and the mass fraction of catalyst in the electrolytic solution is 0 ~ 5%.
2. the serondary lithium battery electrolyte of the anti-thermal runaway of width warm area according to claim 1, it is characterised in that: polymerized monomer
Chain structure with general formula 1 or general formula 2,
General formula 1
R1For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R2For CH2、C2H4、CF2、C2F4、CCl2、C2Cl4、CBr2、 C2Br4One kind；
R3For CH2、CF2、CCl2、CBr2One kind；
R4For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R1And R4It is not simultaneously alkyl, the numerical value that the numerical value of m is 1 ~ 5000, n is 1 ~ 10；
General formula 2
R5For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R6For CH2、CF2、CCl2、CBr2One kind；
R7For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R5And R7It is not simultaneously alkyl, the numerical value that the numerical value of j is 1 ~ 5000, i is 1 ~ 10；
The lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, hexafluoroarsenate lithium, tetrafluoro
Lithium borate, trifluoromethyl sulfonic acid lithium, double fluoromethane sulfimide lithiums one or several kinds；
The additive is one of flame-retardant additive and film for additive or two kinds；Wherein, flame-retardant additive is phosphoric acid
Trimethyl, triethyl phosphate, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester, diphenyl octyl phosphate, pivaloyl amine, three
Paracyanogen acid triallyl, triallyl isocyanate, gamma-butyrolacton, fluorinated ethylene carbonate, three fluoropropylene carbonates, 1,
Tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ether of 1,2,2-, vinyl-three-(methyl ethyl ketone oxime) silane, aminomethyl phenyl dimethyl
One or more of diethoxy silane；Film for additive is vinylacetate, three (trimethyl silane) phosphates, allyl
Ethyl carbonate, methanesulfonic acid propynyl ester, sulfuric acid vinyl ester, 2- phenylimidazole, maleimide, ethylene sulfite, adjacent benzene two
The bromo- benzyl isocyanate ester of phenol carbonic ester, 4-, thiophene, 3,4- ethylenedioxythiophene, hexamethyldisiloxane, N- methyl pyrrole
It coughs up, one or more of ortho-terphenyl, dimethyl acetamide, lithium nitrate, vinylene carbonate；
The solvent is triethylene glycol dimethyl ether, in tetraethyleneglycol dimethyl ether, five ethylene glycol dimethyl ether, succinonitrile, glutaronitrile
It is one or more of；
The catalyst be azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, dibenzoyl peroxide,
N, N- dimethylaniline, n-BuLi, lithium powder, naphthalene sodium, cumyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide,
One or more of tert-butyl hydroperoxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate.
3. a kind of preparation method of the serondary lithium battery electrolyte of the anti-thermal runaway of wide warm area described in claim 1, feature exist
In:
1) one or more than one kinds of polymerized monomers, additive, solvent, catalyst are mixed in a certain ratio, are stirred to complete
Dissolution；
2) lithium salts is added in Xiang Shangshu uniform solution, continues stirring after addition to being completely dissolved, obtains the anti-thermal runaway electricity of wide warm area
Solve liquid；The mass fraction of polymerized monomer in the electrolytic solution is 1%-90%, and the mass fraction of lithium salts in the electrolytic solution is 5%-80%, is added
Adding the mass fraction of agent in the electrolytic solution is 0 ~ 50%, and the mass fraction of solvent in the electrolytic solution is 0 ~ 50%, and catalyst is being electrolysed
Mass fraction in liquid is 0 ~ 5%.
4. a kind of preparation method of the anti-thermal runaway electrolyte of wide warm area according to claim 3, it is characterised in that:
The polymerized monomer has structure shown in general formula 1 or general formula 2:
General formula 1
R1For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R2For CH2、C2H4、CF2、C2F4、CCl2、C2Cl4、CBr2、C2Br4One kind；
R3For CH2、CF2、CCl2、CBr2One kind；
R4For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R1And R4It is not simultaneously alkyl, the numerical value that the numerical value of m is 1 ~ 5000, n is 1 ~ 10；
General formula 2
R5For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R6For CH2、CF2、CCl2、CBr2One kind；
R7For acrylate-based, carbon-carbon double bond, sulfydryl, amino, epoxy alkyl, 1 ~ 10 carbon alkyl one kind；
R5And R7It is not simultaneously alkyl, the numerical value that the numerical value of j is 1 ~ 5000, i is 1 ~ 10；
The lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, hexafluoroarsenate lithium, tetrafluoro
Lithium borate, trifluoromethyl sulfonic acid lithium, double fluoromethane sulfimide lithiums one or several kinds；
The additive is one or both of flame-retardant additive and film for additive；Wherein, flame-retardant additive is tricresyl phosphate
Methyl esters, triethyl phosphate, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester, diphenyl octyl phosphate, pivaloyl amine, trimerization
Cyanic acid triallyl, triallyl isocyanate, gamma-butyrolacton, fluorinated ethylene carbonate, three fluoropropylene carbonates, 1,1,
Tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ether of 2,2-, vinyl-three-(methyl ethyl ketone oxime) silane, aminomethyl phenyl dimethyl two
One or more of Ethoxysilane；Film for additive is vinylacetate, three (trimethyl silane) phosphates, allylic carbon
Acetoacetic ester, methanesulfonic acid propynyl ester, sulfuric acid vinyl ester, 2- phenylimidazole, maleimide, ethylene sulfite, catechol carbon
The bromo- benzyl isocyanate ester of acid esters, 4-, thiophene, 3,4- ethylenedioxythiophene, hexamethyldisiloxane, N- methylpyrrole, neighbour
One or more of terphenyl, dimethyl acetamide, lithium nitrate, vinylene carbonate；
The solvent is triethylene glycol dimethyl ether, in tetraethyleneglycol dimethyl ether, five ethylene glycol dimethyl ether, succinonitrile, glutaronitrile
It is one or more of；
The catalyst be azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, dibenzoyl peroxide,
N, N- dimethylaniline, n-BuLi, lithium powder, naphthalene sodium, cumyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide,
One or more of tert-butyl hydroperoxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate.
5. a kind of a kind of application of the serondary lithium battery electrolyte of the anti-thermal runaway of wide warm area described in claim 1, feature exist
In: application of the width anti-thermal runaway electrolyte of warm area in serondary lithium battery.
6. a kind of serondary lithium battery, including anode, cathode, diaphragm, the electrolyte between positive and negative anodes, it is characterised in that: institute
State the electrolyte electrolyte out of control for the wide warm area heat release of claim 1-5 any claim；The active material of the anode
For cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, ternary material, sulphur, sulfur compound, ferric sulfate lithium, lithium
One of ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide；The active material of cathode is gold
It is compound to belong to lithium, lithium metal alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony carbon composite, tin antimony
One of material, Li-Ti oxide；The diaphragm material is cellulosic separator, polypropylene diaphragm, polyethylene diagrams, glass fibers
Tie up one of diaphragm.
7. a kind of preparation of serondary lithium battery, it is characterised in that: separate positive and negative anodes pole piece with diaphragm, add between positive cathode
Enter the wide warm area heat release of 1-5 any claim electrolyte out of control, seals to obtain serondary lithium battery.
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| CN113381066A (en) * | 2020-03-09 | 2021-09-10 | 多氟多新材料股份有限公司 | High-performance lithium ion battery electrolyte, preparation method thereof and lithium ion battery |
| CN113471537A (en) * | 2021-06-23 | 2021-10-01 | 绍兴铋华科技有限公司 | Flame-retardant electrolyte for lithium iron phosphate battery |
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| CN113471537A (en) * | 2021-06-23 | 2021-10-01 | 绍兴铋华科技有限公司 | Flame-retardant electrolyte for lithium iron phosphate battery |
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