CN105633467A - Electrolyte and lithium ion battery adopting same - Google Patents
Electrolyte and lithium ion battery adopting same Download PDFInfo
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- CN105633467A CN105633467A CN201610192975.8A CN201610192975A CN105633467A CN 105633467 A CN105633467 A CN 105633467A CN 201610192975 A CN201610192975 A CN 201610192975A CN 105633467 A CN105633467 A CN 105633467A
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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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The application relates to the field of lithium ion batteries, in particular to electrolyte and a lithium ion battery adopting the electrolyte. The electrolyte of the present application comprises a non-aqueous organic solvent, a lithium salt and an additive comprising an N-substituted pyrrolidone-boron trifluoride complex compound. The electrolyte can form a good interface film on the surfaces of the anode and the cathode, can reduce the reaction activity of the surface of the anode, and inhibits the oxidative decomposition of the electrolyte on the surface of the anode; meanwhile, the acidic components and transition metal ions generated in the electrolyte are captured by utilizing the characteristic of the Lewis base of the compound, so that the high-temperature storage performance and the cycle performance of the battery under high voltage are improved.
Description
Technical field
The application relates to field of lithium ion battery, specifically, it relates to a kind of electrolytic solution and adopt the lithium ion battery of this electrolytic solution.
Background technology
The electronic mobile device such as notebook computer, mobile phone, handheld game machine, panel computer can realize more and more functions, and the utilisation technology of the aspect such as electromobile, intelligent grid also reaches its maturity. The flying power of the lithium ion battery as its main drive energy is required also more and more higher by people. Improve the research focus that energy density becomes lithium ion battery.
For the lithium ion battery that positive electrode material is nickel-cobalt-manganese ternary material, promoting charging is the effective ways increasing energy capacity of battery density by voltage. But when improving the voltage of lithium ion battery, when especially charging voltage reaches more than 4.35V, owing to de-lithium ratio increases, the structural stability of positive electrode material reduces, and easily undergoes phase transition reduction positive electrode capacity; Transition metal dissolves aggravation simultaneously, moves to negative pole and destroys SEI, produce a large amount of reducing gas, consumes electrolytic solution. Owing to voltage has exceeded electrolyte oxidation reduction window, will there is oxidizing reaction in electrolytic solution, consume electrolytic solution fast on positive pole, produce a large amount of by product or gas. Due to the existence of above two kinds of effects, lithium ion battery is in charging when voltage is higher than charge and discharge during 4.35V, and inducing capacity fading is obviously accelerated.
In actual use, electronic product also faces and uses the environment for use temperature rising etc. of heating or lithium ion battery that lithium ion battery all may be made to be in the condition of high temperature as lasting, and at high temperature, electrolytic solution will be subject to stricter test, owing to the dilatational strain of lithium ion battery causes inside lithium ion cell to be short-circuited or lithium ion battery packaging is burst and caused flammable electrolytic solution to be revealed time serious, thus cause the security incidents such as fire. It is thus desirable to improve the oxidation potential of electrolytic solution further, effective technology solves the decomposition of electrolytic solution, the problem of lithium ion battery flatulence. Given this, it is necessary to develop the high-voltage electrolyte of a kind of high temperature circulation.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of electrolytic solution.
2nd goal of the invention of the application is to propose a kind of lithium ion battery adopting this electrolytic solution.
In order to complete the object of the application, the technical scheme of employing is:
A kind of electrolytic solution, comprises non-aqueous organic solvent, lithium salt and additive, and described additive comprises N substituted pyrrolidone-boron trifluoride coordination compound.
Preferably, at least one that described N substituted pyrrolidone-boron trifluoride coordination compound is selected from the compound such as formula structural formula shown in I:
Wherein, R is selected from substituted or unsubstituted C1��30Alkyl, substituted or unsubstituted C2��30Alkene base, substituted or unsubstituted C2��30Alkynes base, substituted or unsubstituted C6��26Aryl;
Substituting group is selected from halogen.
Preferably, R is selected from substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C2��20Alkene base; R is preferably the C of straight or branched1��12Alkyl, C2��12Alkene base, C3��12Cycloalkyl.
Preferably, at least one that described N substituted pyrrolidone-boron trifluoride coordination compound is selected from boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N-ethyl pyrrolidone, boron trifluoride-N-propyl pyrrole alkane ketone, boron trifluoride-N-isopropylpyrrolidine ketone, boron trifluoride-NVP, boron trifluoride-N-propenyl pyrrolidone, boron trifluoride-N-pseudoallyl pyrrolidone, boron trifluoride-NOP, boron trifluoride-N-cyclohexyl pyrrolidone; At least one in preferred boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N-ethyl pyrrolidone, boron trifluoride-NVP.
Preferably, the quality of described N substituted pyrrolidone-boron trifluoride coordination compound is the 0.1%��5% of the total mass of the electrolytic solution of lithium ion battery.
Preferably, the at least one that described organic solvent is selected from NSC 11801, propylene carbonate, butylene, fluorinated ethylene carbonate, Methyl ethyl carbonate, methylcarbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-butyrolactone, methyl propionate, methyl-butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl butyrate.
Preferably, described lithium salt is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, four fluorine oxalic acid Trilithium phosphates, two trifluoromethanesulfonimide lithium, two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, LiN (SO2RF)2��LiN(SO2F)(SO2RF) at least one, wherein, RF=CnF2n+1, n is the integer of 1��10; Preferred LiPF6��LiN(SO2RF)2In at least one.
Preferably, the concentration of described lithium salt in the electrolytic solution of lithium ion battery is 0.3M��1.8M.
The application relates to a kind of lithium ion battery, comprising: positive plate, the positive pole diaphragm containing positive electrode active materials comprising plus plate current-collecting body and being arranged on plus plate current-collecting body; Negative plate, the cathode membrane containing negative active core-shell material comprising negative current collector and being arranged on negative current collector; Barrier film, is interval between adjacent positive/negative plate; Electrolytic solution; And package foil; It is characterized in that, described electrolytic solution is the electrolytic solution of the application.
The useful effect that the technical scheme of the application can reach is:
N substituted pyrrolidone-boron trifluoride coordination compound is joined in lithium-ion battery electrolytes by the application, it is possible to improve high temperature circulation and the memory property of high-voltage lithium ion batteries. The electrolysis additive of the application can be interacted by boron atom in boron trifluoride structure and positive pole Sauerstoffatom, and the ketonic oxygen of N substituted pyrrolidone and nitrogen-atoms can provide the surface stability of positive electrode material under the coordination lifting high-voltage of electronics and transition metal simultaneously; The formation of solid electrolyte film is participated in negative terminal surface. N substituted pyrrolidone-boron trifluoride coordination compound all forms good interfacial film on positive and negative electrode surface, reduce the reactive behavior of positive electrode surface, improve the oxidizing potential of electrolytic solution, suppress electrolytic solution in the oxygenolysis of positive electrode surface, improve high temperature storage volts lost and produce gas.
The ketonic oxygen of the N substituted pyrrolidone of the application and nitrogen-atoms can provide the coordination of electronics and transition metal can also catch the transition metal ion of positive pole stripping in the electrolytic solution, prevent transition metal ion from destroying negative pole solid electrolyte film, boron trifluoride can also dissolve the lithium fluoride being deposited in electrode duct, form solvable lithium salt, reduce the lithium fluoride deposition of electrode surface, alleviating the blocking in electrode duct, these characteristics are all conducive to promoting high-temperature cycle life and memory property.
In addition, the additive of the application can effectively promote the wetting property of electrode slice, this is because N substituted pyrrolidone comprises hydrophobic side chain (substituting group on nitrogen-atoms) and hydrophilic head (pyrrolidone ring), hydrophobic side chain and carbon material used as anode interact, and reduce negative terminal surface tension force. The interaction of hydrophilic head and positive electrode material promotes the wetting property of electrolytic solution.
Below in conjunction with specific embodiment, set forth the application further. It will be understood that these embodiments are only not used in the scope of restriction the application for illustration of the application.
Embodiment
The application relates to a kind of electrolytic solution, comprises non-aqueous organic solvent, lithium salt and additive, and additive comprises N substituted pyrrolidone-boron trifluoride coordination compound.
N substituted pyrrolidone-boron trifluoride coordination compound refers to the coordination compound that N substituted pyrrolidone molecule and boron trifluoride are formed, boron trifluoride is negatively charged ion, N substituted pyrrolidone is positively charged ion, and whole N substituted pyrrolidone-boron trifluoride coordination compound is electric neutrality.
As a kind of improvement of the application's electrolytic solution, at least one that N substituted pyrrolidone-boron trifluoride coordination compound is selected from the compound such as formula structural formula shown in II:
Wherein, R is selected from substituted or unsubstituted C1��30Alkyl, substituted or unsubstituted C2��30Alkene base, substituted or unsubstituted C2��30Alkynes base, substituted or unsubstituted C6��26Aryl;
R ', R ", R " ' independent be separately selected from hydrogen atom, halogen, C respectively1��6Alkyl, C1��6Alkoxyl group, C1��6Acyloxy;
Substituting group is selected from halogen.
Halogen in the application is selected from fluorine, chlorine, bromine; It is preferably fluorine.
As a kind of improvement of the application's electrolytic solution, at least one that N substituted pyrrolidone-boron trifluoride coordination compound is selected from the compound such as formula structural formula shown in I:
Wherein, R is selected from substituted or unsubstituted C1��30Alkyl, substituted or unsubstituted C2��30Alkene base, substituted or unsubstituted C2��30Alkynes base, substituted or unsubstituted C6��26Aryl;
Substituting group is selected from halogen.
As a kind of improvement of the application's electrolytic solution, R is selected from substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C2��20Alkene base; R is preferably the C of straight or branched1��12Alkyl, C2��12Alkene base, C3��12Cycloalkyl.
In this application, carbonatoms is the alkyl of 1��30, and alkyl can be chain-like alkyl, it is possible to be cycloalkyl, the hydrogen being positioned on the ring of cycloalkyl can be replaced by alkyl, and in described alkyl, the preferred lower value of carbonatoms is 2,3,4,5, it is preferable that higher limit be 3,4,5,6,8,10,12,14,16,18,20,22,24,26,28. Preferably, carbonatoms is selected to be the alkyl of 1��20, further preferably, selecting carbonatoms to be the chain-like alkyl of 1��12, carbonatoms is the cycloalkyl of 3��12, still more preferably, selecting carbonatoms to be the chain-like alkyl of 1��6, carbonatoms is the cycloalkyl of 5��7. As the example of chain-like alkyl, specifically can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, own base, 2-methyl-amyl group, 3-methyl-amyl group, 1,1,2-trimethyl-propyl, 3,3 ,-dimethyl-butyl, n-heptyl, 2-heptyl, 3-heptyl, the own base of 2-methyl, the own base of 3-methyl, octyl group, nonyl, the last of the ten Heavenly stems base. As the example of cycloalkyl, specifically can enumerate: cyclopentyl, cyclohexyl, ring octyl group.
In this application, carbonatoms be 2��30 alkene base can be ring-type alkene base, it is possible to be chain shape alkene base. In addition, in alkene base, the number of double bond is preferably 1. In described alkene base, the preferred lower value of carbonatoms is 3,4,5, it is preferable that higher limit be 3,4,5,6,8,10,12,14,16,18,20,22,24,26,28. Preferably, selection carbonatoms is the alkene base of 2��20, and further preferably, selection carbonatoms is the alkene base of 2��12, and still more preferably, selection carbonatoms is the alkene base of 2��6. As the example of alkene base, specifically can enumerate: vinyl, allyl group, pseudoallyl, pentenyl, cyclohexenyl, cycloheptenyl, cyclooctene base.
In this application, carbonatoms is the aryl of 6��26, such as phenyl, benzene alkyl, at least also can be replaced by alkyl or alkene base containing aryl such as xenyl, condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and the condensed-nuclei aromatics base of a phenyl. Preferably, select carbonatoms to be the aryl of 6��16, further preferably, select carbonatoms to be the aryl of 6��14, still more preferably, select carbonatoms to be the aryl of 6��9. As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, adjacent tolyl, a tolyl.
As a kind of improvement of the application's electrolytic solution, at least one that N substituted pyrrolidone-boron trifluoride coordination compound is selected from following compound:
Boron trifluoride-N-Methyl pyrrolidone;
Boron trifluoride-N-ethyl pyrrolidone;
Boron trifluoride-N-propyl pyrrole alkane ketone;
Boron trifluoride-N-isopropylpyrrolidine ketone;
Boron trifluoride-NVP;
Boron trifluoride-N-propenyl pyrrolidone;
Boron trifluoride-N-pseudoallyl pyrrolidone;Boron trifluoride-NOP;
Boron trifluoride-N-cyclohexyl pyrrolidone.
And preferably: at least one in boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N-ethyl pyrrolidone, boron trifluoride-NVP.
As a kind of improvement of the application's electrolytic solution, at least one that N substituted pyrrolidone-boron trifluoride coordination compound can also be selected from following compound:
As a kind of improvement of the application's electrolytic solution, the quality of N substituted pyrrolidone-boron trifluoride coordination compound is the 0.1%��5% of the total mass of electrolytic solution.
When boron trifluoride-N-Methyl pyrrolidone title complex content is greater than 5%, electrolyte system viscosity is caused to become big, the interfacial film simultaneously formed on positive and negative electrode surface is excessively thick, have impact on the cycle performance of lithium ion battery, but memory property is still improved further, this is because the boron trifluoride of high-content-N-Methyl pyrrolidone title complex can form good interfacial film on positive and negative electrode surface on the one hand, reduce the reactive behavior of positive electrode surface, simultaneously, N substituted pyrrolidone-boron trifluoride coordination compound contains Lewis base, the sour gas produced can be neutralized in storage process, such as PF5��HF��CO2Deng. When boron trifluoride-N-Methyl pyrrolidone title complex mass percentage in the electrolytic solution, < when 0.1%, then very few boron trifluoride-N-Methyl pyrrolidone title complex is not obvious to the improvement of performance of lithium ion battery.
In above-mentioned electrolytic solution, non-aqueous organic solvent is selected from least one of carbonate products, carbonate, and wherein, carbonate products can be linear carbonate, it is possible to be cyclic carbonate.
As the example of organic solvent, can enumerate: at least one in NSC 11801, propylene carbonate, butylene, fluorinated ethylene carbonate, Methyl ethyl carbonate, methylcarbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-butyrolactone, methyl propionate, methyl-butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate.
Non-aqueous organic solvent can also be selected from methyl acrylate, dimethyl sulfite, diethyl sulfite, acid anhydrides, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, one or more in dinethylformamide, methyl-sulphoxide, dimethyl sulfide, tetrahydrofuran (THF). In above-mentioned electrolytic solution, lithium salt can be organic lithium salt, it is possible to is inorganic lithium salt, specifically, can contain at least one in fluorine element, boron, phosphoric in lithium salt. Preferably, lithium salt is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), four fluorine oxalic acid Trilithium phosphate (LiTFOP), LiN (SO2RF)2��LiN(SO2F)(SO2RF), two trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), two (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) at least one in (being abbreviated as LiDFOB), wherein, substituent RF=CnF2n+1Saturated perfluoroalkyl, n is the integer of 1��10, and 2n+1 is greater than the integer of zero. It is particularly preferably LiPF6And/or LiN (SO2RF)2. Described lithium salt concentration in the electrolytic solution is 0.5M��2M (M=mol L-1)��
In this application, the preparation method of electrolytic solution selects ordinary method, such as, can organic solvent, lithium salt and additive be mixed.
Another object of the application is to provide a kind of lithium ion battery, and this lithium ion battery comprises the electrolytic solution of the application, the positive plate containing positive electrode active materials, the negative plate containing negative active core-shell material and barrier film.
In above-mentioned lithium ion battery, positive plate also comprises binding agent and conductive agent, is coated on plus plate current-collecting body by the anode sizing agent including positive electrode active materials, binding agent and conductive agent, obtains positive plate after anode sizing agent drying. Same, the cathode size including negative active core-shell material, binding agent and conductive agent is coated on negative current collector, after cathode size drying, obtains negative plate.
Preferably, positive electrode active materials is selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, lithium manganate (LiMnO2) at least one, such as cobalt acid lithium and the mixture of lithium-nickel-manganese-cobalt ternary material can be used as positive electrode active materials. As the example of cobalt nickel lithium manganate ternary material, specifically can enumerate: LiNi1/3Co1/3Mn1/3O2��LiNi0.5Co0.2Mn0.3O2��LiNi0.6Co0.2Mn0.2O2��
Preferably, negative active core-shell material is carbon material and/or silicon materials.
In above-mentioned lithium ion battery, the concrete kind of lithium battery diaphragm is not subject to concrete restriction, can be any diaphragm material used in existing lithium ion battery, such as polyethylene, polypropylene, polyvinylidene difluoride (PVDF) and their multilayer complex films, but it is not limited only to these.
The charging upper limit stopping potential of the lithium ion battery of the application is 4.35V��4.6V.
Embodiment 1��30
(1) preparation of the positive plate of lithium ion battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi0.6Co0.2Mn0.2O2), conductive agent Super-P, caking agent PVDF in mass ratio 97.2:1.3:1.5 be dissolved in solvent N-methyl pyrilidone to mix make anode sizing agent, being uniformly coated on the tow sides of current collector aluminum foil by anode sizing agent afterwards, glue spread is 0.0102g/cm2, carry out colding pressing after drying at 85 DEG C subsequently, trimming, cut-parts, point bar, afterwards dry 4h under 85 DEG C of vacuum conditions, soldering polar ear, makes the positive plate of lithium ion battery.
(2) preparation of the negative plate of lithium ion battery
By negative active core-shell material synthetic graphite, conductive agent Super-P, thickening material CMC, caking agent SBR in mass ratio 95.4:1.2:1.2:2.2 be dissolved in solvent deionized water to mix make cathode size, being uniformly coated on the tow sides of copper foil of affluxion body by cathode size afterwards, glue spread is 0.0071g/cm2, carry out colding pressing after drying at 85 DEG C subsequently, trimming, cut-parts, point bar, afterwards dry 4h under 110 DEG C of vacuum conditions, soldering polar ear, makes the negative plate of lithium ion battery.
(3) preparation of the electrolytic solution of lithium ion battery
The electrolytic solution of lithium ion battery is with the LiPF of 1mol/L6For lithium salt, taking the mixture of NSC 11801 (EC), Methyl ethyl carbonate (EMC) as non-aqueous organic solvent, wherein the mass ratio of electrolyte solvent part EC:EMC is 30:70. In addition, also containing additive in the electrolytic solution of lithium ion battery, content and the title of additive are as shown in table 1.
(4) preparation of lithium ion battery
By the positive plate of the lithium ion battery prepared according to previous process, negative plate and barrier film (PE film, containing ceramic coating) through winding process, to be made into thickness be 5.7mm, width be 16mm, length is the battery core of 33mm, wherein this battery core leaves long airbag, to observe it producing gas. And at 85 DEG C vacuum bakeout 14h (vacuum tightness <-0.08MPa), inject electrolytic solution, leave standstill 24h, afterwards by the constant current charge of 0.05C (11mA) to 3.4V, taking off battery, then first to carry out vacuum pre-packaged so that degasification; Again with the constant current charge of 0.05C (11mA) to 4.5V, then again battery is taken off and carry out second time degasification; Then it is discharged to 3V with the constant current of 0.5C (110mA), repeats 2 discharge and recharges, finally with the constant current charge of 0.5C (110mA) to 3.85V, complete the preparation of lithium ion battery.
Comparative example 1��14
In comparative example 1, prepare lithium ion battery according to the method for embodiment 1, just in the preparation (i.e. step (3)) of the electrolytic solution of lithium ion battery, do not add any additive; In comparative example 2��14, in the preparation (i.e. step (3)) of the electrolytic solution of lithium ion battery, being also added with additive, content and the title of additive are as shown in table 1.
Electrolytic solution in the application and the test process of lithium ion battery thereof and test result.
(1) the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, first with the constant current of 0.5C to lithium ion cell charging to 4.5V, electric current is charged to as 0.025C further taking 4.5V constant voltage, then with the constant current of 0.5C, lithium ion battery is discharged to 2.8V, this is a charge and discharge cycles process, and this loading capacity is the loading capacity of formula 1 circulation. Lithium ion battery is carried out in a manner described cycle charge discharge electrical testing, gets the loading capacity of the 100th circulation.
Capability retention (%) after lithium ion battery 100 circulations=(loading capacity of the loading capacity/formula of the 100th circulation 1 circulation) �� 100%.
(2) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, first with the constant current of 0.5C to lithium ion cell charging to 4.5V, electric current is charged to as 0.025C further taking 4.5V constant voltage, then lithium ion battery drainage has been surveyed in deionized water at original volume is placed on 60 DEG C and stored 30 days, after end to be stored, test lithium ion battery volume change after storage at high temperatures.
Volume change (%) after high-temperature lithium ion battery storage=(volume before the volume after high-temperature lithium ion battery storage/high-temperature lithium ion battery storage) �� 100%.
The performance test results of embodiment and comparative example is as shown in table 1:
Table 1:
The performance test results analysis of lithium ion battery:
As can be seen from the contrast of embodiment 1-6 and comparative example 1-3, add the lithium ion battery of boron trifluoride-N-Methyl pyrrolidone title complex, than the lithium ion battery of the comparative example 1 not adding any additive, there is good high temperature cyclic performance and high-temperature storage performance.
When boron trifluoride-N-Methyl pyrrolidone title complex content is greater than 5% (comparative example 3), worsening occurs in its cycle performance, may be cause electrolyte system viscosity to become big because boron trifluoride-N-Methyl pyrrolidone title complex occupies the excessive ratio of non-aqueous organic solvent, the interfacial film simultaneously formed on positive and negative electrode surface is excessively thick, have impact on the cycle performance of lithium ion battery, but memory property is still improved further, this is because the boron trifluoride of high-content-N-Methyl pyrrolidone title complex can form good interfacial film on positive and negative electrode surface on the one hand, reduce the reactive behavior of positive electrode surface, boron trifluoride-N-Methyl pyrrolidone title complex contains Lewis base simultaneously, the sour gas produced can be neutralized in storage process, such as PF5��HF��CO2Deng. When the mass percentage of boron trifluoride-N-Methyl pyrrolidone title complex in the electrolytic solution of lithium ion battery, < time 0.1% (comparative example 2), then very few boron trifluoride-N-Methyl pyrrolidone title complex is not obvious to the improvement of the performance of lithium ion battery. With reason, similar result can be seen from the contrast of embodiment 7-30 and comparative example 4-10.
It may be seen that N substituted pyrrolidone used in this application has better high temperature circulation and high-temperature storage performance than ether or methylcarbonate from embodiment 4,10,16,22 and 28 and the contrast of comparative example 11 and 12. May be because N substituted pyrrolidone has Lewis base, it is possible to the acidic components produced in neutralization circulation storage process, catch the transition metal ion of positive pole stripping, prevent negative pole solid electrolyte film from being destroyed, thus improve circulation storage stability.
It may be seen that presoma R base pyrrolidone used in this application has better high temperature circulation and high-temperature storage performance than DMAC N,N' dimethyl acetamide from the contrast of embodiment 4,10,16,22 and 28 and comparative example 13. May be because the ring texture of N substituted pyrrolidone can in negative pole ring-opening polymerization; participate in the generation of negative pole solid electrolyte film; and N substituted pyrrolidone does not have hydrogen atom on nitrogen-atoms; which reduce the existence of reactive hydrogen in electrolytic solution; decrease the possibility that the materials such as HF generate; protection positive electrode material is not corroded, and improves the cycle performance of battery.
It may be seen that the application uses boron trifluoride-methyl-2-pyrrolidone to have better high temperature circulation than independent methyl-2-pyrrolidone from the contrast of embodiment 4 and comparative example 14. May be that boron trifluoride-methyl-2-pyrrolidone can form more stable positive pole solid electrolyte film; protection positive electrode surface is stablized; the lithium fluoride being deposited on positive and negative electrode surface can be dissolved simultaneously, alleviate the situation that positive and negative electrode duct is blocked, extend the cycle life of battery.
Embodiment 31��36
According to the preparation method of embodiment 1, preparing lithium ion battery with the compound of the additive shown in table 2 and content, the capability retention after the high temperature circulation that test obtains, the cubical expansivity after high temperature storage are as shown in table 2.
Table 2:
It thus is seen that a kind of lithium ion battery of providing of the application and electrolytic solution thereof and new additive agent, it is possible to form good interfacial film on positive and negative electrode surface, it is possible to reduce the reactive behavior of positive electrode surface, suppress electrolytic solution in the oxygenolysis of positive electrode surface; Utilize in this compound the characteristic of contained Lewis base to catch the acidic components and transition metal ion that produce in the electrolytic solution, to improve battery high-temperature storage performance under high voltages and cycle performance simultaneously.
Being more than the concrete explanation of the better embodiment of the application, but the application is not limited to described embodiment, some distortion or replacement compound are all included in the application's claim limited range. In addition, the application employs some specific term, but these terms are just for convenience of description, and the application does not form any restriction.
Claims (10)
1. an electrolytic solution, comprises non-aqueous organic solvent, lithium salt and additive, it is characterised in that, described additive comprises N substituted pyrrolidone-boron trifluoride coordination compound.
2. electrolytic solution according to claim 1, it is characterised in that, at least one that described N substituted pyrrolidone-boron trifluoride coordination compound is selected from the compound such as formula structural formula shown in I:
Wherein, R is selected from substituted or unsubstituted C1��30Alkyl, substituted or unsubstituted C2��30Alkene base, substituted or unsubstituted C2��30Alkynes base, substituted or unsubstituted C6��26Aryl;
Substituting group is selected from halogen.
3. electrolytic solution according to claim 2, it is characterised in that, R is selected from substituted or unsubstituted C1��20Alkyl, substituted or unsubstituted C2��20Alkene base; R is preferably the C of straight or branched1��12Alkyl, C2��12Alkene base, C3��12Cycloalkyl.
4. electrolytic solution according to claim 1, it is characterized in that, at least one that described N substituted pyrrolidone-boron trifluoride coordination compound is selected from boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N-ethyl pyrrolidone, boron trifluoride-N-propyl pyrrole alkane ketone, boron trifluoride-N-isopropylpyrrolidine ketone, boron trifluoride-NVP, boron trifluoride-N-propenyl pyrrolidone, boron trifluoride-N-pseudoallyl pyrrolidone, boron trifluoride-NOP, boron trifluoride-N-cyclohexyl pyrrolidone; At least one in preferred boron trifluoride-N-Methyl pyrrolidone, boron trifluoride-N-ethyl pyrrolidone, boron trifluoride-NVP.
5. electrolytic solution according to claim 1, it is characterised in that, the quality of described N substituted pyrrolidone-boron trifluoride coordination compound is the 0.1%��5% of electrolytic solution total mass.
6. electrolytic solution according to claim 1, it is characterized in that, the at least one that described non-aqueous organic solvent is selected from NSC 11801, propylene carbonate, butylene, fluorinated ethylene carbonate, Methyl ethyl carbonate, methylcarbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-butyrolactone, methyl propionate, methyl-butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl butyrate.
7. electrolytic solution according to claim 1, it is characterized in that, described lithium salt is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, four fluorine oxalic acid Trilithium phosphates, two trifluoromethanesulfonimide lithium, two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, LiN (SO2RF)2��LiN(SO2F)(SO2RF) at least one, wherein, RFFor-CnF2n+1, n is the integer of 1��10; Preferred LiPF6��LiN(SO2RF)2In at least one.
8. electrolytic solution according to claim 1, it is characterised in that, described lithium salt concentration in the electrolytic solution is 0.3M��1.8M.
9. a lithium ion battery, comprising: positive plate, the positive pole diaphragm containing positive electrode active materials comprising plus plate current-collecting body and being arranged on plus plate current-collecting body; Negative plate, the cathode membrane containing negative active core-shell material comprising negative current collector and being arranged on negative current collector; Barrier film, is interval between adjacent positive/negative plate; Electrolytic solution; And package foil; It is characterized in that, described electrolytic solution is the electrolytic solution according to any one of claim 1��8.
10. lithium ion battery according to claim 9, it is characterized in that, the at least one that described positive electrode active materials is selected from cobalt acid lithium, cobalt nickel lithium manganate ternary material, LiFePO 4 and lithium manganate, described negative active core-shell material is carbon material and/or silicon materials.
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Effective date of registration: 20201119 Address after: 213300 No. 1000 North Avenue, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province Patentee after: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. (JIANGSU) Address before: 352100, Xingang Road, Ningde Town, Jiaocheng District, Fujian, 1 Patentee before: Contemporary Amperex Technology Co.,Ltd. |